Thermostimulative shape memory effect of linear low‐density polyethylene/polypropylene (LLDPE/PP) blends compatibilized by crosslinked LLDPE/PP blend (LLDPE–PP)

A novel linear low‐density polyethylene (LLDPE)/polypropylene (PP) thermostimulative shape memory blends were prepared by melt blending with moderate crosslinked LLDPE/PP blend (LLDPE–PP) as compatibilizer. In this shape memory polymer (SMP) blends, dispersed PP acted as fixed phase whereas continuous LLDPE phase acted as reversible or switch phase. LLDPE–PP improved the compatibility of LLDPE/PP blends as shown in scanning electron microscopic photos. Dynamic mechanical analysis test showed that the melt strengths of the blends were enhanced with increasing LLDPE–PP content. A shape memory mechanism for this type of SMP system was then concluded. It was found that when the blend ratio of LLDPE/PP/LLDPE–PP was 87/13/6, the blend exhibited the best shape memory effect at stretch ratio of 80%, stretch rate of 25 mm/min, and recovery temperature of 135°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

废胶粉/高密度聚乙烯热塑性弹性体的结构与性能

主要考察了橡塑比、胶粉含量、相容剂C含量的变化对TPE力学性能的影响．胶粉含量对TPE的流动性能、挤出物的表观的影响。结果表明：随着橡塑比的增加，TPE的拉伸强度逐渐降低．拉断伸长率逐渐增加。胶粉含量的增加。TPE的力学性能逐渐降低。TPE的流动性、挤出物的表面随着胶粉含量的降低而变好。随着相容剂C的增加。拉伸强度呈现先增加后减少的趋势，但拉断伸长率逐渐增加。     

PVC／胶粉热塑性弹性体的制备与性能研究

以聚氯乙烯(PVC)和胶粉为主要原料,采用共混的方法制备了PVC／胶粉热塑性弹性体,研究了胶粉的改性剂、PVC的改性剂和胶粉的用量等对PVC／胶粉热塑性弹性体性能的影响,并与国标GB／T 18173.1–2012所要求的性能进行比对。研究结果表明,使用橡胶再生剂RV改性胶粉所制得的PVC／胶粉热塑性弹性体综合性能最优;使用乙烯–乙酸乙烯酯塑料(EVAC)、苯乙烯–丁二烯–苯乙烯塑料(SBS)改性PVC时,EVAC的改性效果优于SBS,使用15份EVAC所制得的PVC／胶粉热塑性弹性体具有更佳的力学性能、耐老化性能,且满足国标要求;随着胶粉用量的增加,PVC／胶粉热塑性弹性体的综合力学性能下降,耐老化性能提高,使用30份改性胶粉时性价比最高,同时满足国标GB／T 18173.1–2012要求。     

Mg(OH)_2/红磷复配阻燃NR/LLDPE TPV的研究

研究了硅烷偶联剂KH-550和甲基丙烯酸缩水甘油酯/苯乙烯/过氧化二异丙苯(GMA/St/DCP)多单体"原位"增容改性Mg(OH)2/红磷复配阻燃剂对天然橡胶/线性低密度聚乙烯动态硫化热塑性弹性体(NR/LLDPE TPV)的阻燃效果、静态和动态力学性能及耐热分解性能的影响。结果表明,"原位"增容改性有利于改善NR/LLDPE TPV的阻燃性能和力学性能;当m[Mg(OH)2]/m(红磷)=80/8时,"原位"增容改性阻燃NR/LLDPE TPV的氧的最低浓度(LOI)达到25.6%(体积分数),燃烧时无黑烟和熔滴滴落现象,力学性能保持率较高并具有较好的耐寒性和耐热分解性能。     

The Effect of Epoxidized Natural Rubber (ENR-50) or Polyethylene Acrylic Acid (PEA) as Compatibilizer on Properties of Ethylene Vinyl Acetate (EVA)/Natural Rubber (SMR L) Blends

The effect of epoxidized natural rubber (ENR) or polyethylene acrylic acid (PEA) as a compatibilizer on properties of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends was studied. 5 wt.% of compatibilizer was employed in EVA/SMR L blend and the effect of compatibilizer on tensile properties, thermal properties, swelling resistance, and morphological properties were investigated. Blends were prepared by using a laboratory scale of internal mixer at 120°C with 50 rpm of rotor speed. Tensile properties, thermal properties, thermo-oxidative aging resistance, and oil swell resistance were determined according to related ASTM standards. The compatibility of EVA/SMR L blends with 5 wt.% of compatibilizer addition or without compatibilizing agent was compared. The EVA/SMR L blend with compatibilizer shows substantially improvement in tensile properties compared to the EVA/SMR L blend without compatibilizer. Compatibilization had reduced interfacial tension and domain size of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends.     

Compatibilizer in waste tire powder and low‐density polyethylene blends and the blends modified asphalt

With the increasing ratio of waste tire powder (WTP) to low‐density polyethylene (LDPE), the hardness and tensile strength of the WTP/LDPE blends decreased while the elongation at break increased. Five kinds of compatibilizers, such as maleic anhydride‐grafted polyethylene (PE‐g‐MA), maleic anhydride‐grafted ethylene‐octene copolymer (POE‐g‐MA), maleic anhydride‐grafted linear LDPE, maleic anhydride‐grafted ethylene vinyl‐acetate copolymer, and maleic anhydride‐grafted styrene‐ethylene‐butylene‐styrene, were incorporated to prepare WTP/LDPE blends, respectively. PE‐g‐MA and POE‐g‐MA reinforced the tensile stress and toughness of the blends. The toughness value of POE‐g‐MA incorporating blends was the highest, reached to 2032.3 MJ/m³, while that of the control was only 1402.9 MJ/m³. Therefore, POE‐g‐MA was selected as asphalt modifier. The toughness value reached to the highest level when the content of POE‐g‐MA was about 8%. Besides that the softening point of the modified asphalt would be higher than 60°C, whereas the content of WTP/LDPE blend was more than 5%, and the blends were mixed by stirring under the shearing speed of 3000 rpm for 20 min. Especially, when the blend content was 8.5%, the softening point arrived at 82°C, contributing to asphalt strength and elastic properties in a wide range of temperature. In addition, the swelling property of POE‐g‐MA/WTP/LDPE blend was better than that of the other compalibitizers, which indicated that POE‐g‐MA /WTP/LDPE blend was much compatible with asphalt. Also, the excellent compatibility would result in the good mechanical and processing properties of the modified asphalt. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PE-LLD-g-(GMA-co-St)对PLA/PE-LLD共混体系的反应性增容研究

在聚乳酸(PLA)中加入线形低密度聚乙烯(PE-LLD)进行增韧,并通过相容剂 PE-LLD-g-(GMA-co-St)增容PLA 和 PE-LLD。采用红外光谱、动态流变测试和扫描电子显微镜对共混物进行了表征,测试了共混物的冲击强度。结果表明,加入 PE-LLD-g-(GMA-co-St)能明显提高 PLA/PE-LLD 的冲击韧性,最高比 PLA/PE-LLD 简单共混物提高了144%,熔体的损耗模量G″明显增大,PE-LLD 分散相在 PLA 基体中有更加细微的分散,界面更加模糊,PE-LLD-g-(GMA-co-St)在共混体系中起到了反应性增容作用。     

Thermoplastic Polyurethane Elastomers with Aliphatic Hard Segments Based on Plant‐Oil‐Derived Long‐Chain Diisocyanates

Novel plant‐oil‐derived long‐chain (C₁₉ and C₂₃) α,ω‐diisocyanates, optionally in combination with the corresponding long‐chain diols, provide entirely aliphatic hard segments in segmented thermoplastic polyurethane elastomers (TPUs), with carbohydrate‐based poly(trimethylene glycol) soft segments. Compared to materials based on a mid‐chain monomer analog, phase separation is higher due to an increased flexibility of the aliphatic segments. Although melting points are slightly lower than for HDPE, the long‐chain TPU's solid‐state structure is still dominated by hydrogen‐bonding.     

Preparation of dynamically vulcanized thermoplastic elastomer nanocomposites based on LLDPE/reclaimed rubber

Dynamically vulcanized thermoplastic elastomers nanocomposites (TPV nanocomposites) based on linear low density polyethylene (LLDPE)/reclaimed rubber/organoclay were prepared via one‐step melt blending process. Maleic anhydride grafted polyethylene (PE‐g‐MA) was used as a compatibilizing agent. The effects of reclaimed rubber content (10, 30, and 50 wt %), nanoclay content (3, 5, and 7 wt %), and PE‐g‐MA on the microstructure, thermal behavior, mechanical properties, and rheological behavior of the nanocomposites were studied. The TPV nanocomposites were characterized by X‐ray diffraction, transmission electron microscopy, scanning electron microscopy (SEM), differential scanning calorimeter, mechanical properties, and rheometry in small amplitude oscillatory shear. SEM photomicrographs of the etched samples showed that the elastomer particles were dispersed homogeneously throughout the polyethylene matrix and the size of rubber particles was reduced with introduction of the organoclay particles and compatibilizer. The effects of different nanoclay contents, different rubber contents, and compatibilizer on mechanical properties were investigated. Increasing the amount of nanoclay content and adding the compatibilizer result in an improvement of the tensile modulus of the TPV nanocomposite samples. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Maleated Natural Rubber as a Coupling Agent for Recycled High Density Polyethylene/Natural Rubber/Kenaf Powder Biocomposites

Kenaf powder (KP) was incorporated into recycled high density polyethylene (rHDPE)/natural rubber (NR) blend using an internal mixer at 165°C and rotor speed of 50 rpm. The tensile strength and elongation at break of the composites decreased, while the tensile modulus increased with increasing filler loading. The water absorption was found to increase as the filler content increased. The maleic anhydride grafted natural rubber was prepared and used to enhance the composites performance. The addition of MANR as a coupling agent improved the tensile properties of rHDPE/NR/KP biocomposites. The water absorption was also reduced with the addition of MANR.     

胶粉/低密度聚乙烯复合材料的性能研究简

采用全轮胎废胶粉(WRP)/低密度聚乙烯(LDPE)(并用比65/35)制备橡塑复合材料。研究增容剂和交联体系对WRP/LDPE复合材料物理性能的影响。结果表明:乙烯-乙酸乙烯酯对WRP/LDPE复合材料的增容效果较好;交联体系采用过氧化二异丙苯且用量为1份时WRP/LDPE复合材料物理性能较好。     

Structure‐property relationships of LLDPE—highly filled with aluminum hydroxide

The mechanical performance, rheological behavior, and phase morphology of linear low‐density polyethylene (LLDPE) highly loaded with aluminum hydroxide [Al(OH)₃] were investigated. It was found that titanate surface‐active agent and ethylene‐vinyl acetate copolymer (EVA) improve the processing and ductile properties of the composite remarkably but are accompanied by the deterioration of the tensile strength. Addition of vinyl triethoxy silane (VTEO) and dicumyl peroxide (DCP) improves the tensile strength of the composite because of the silane crosslinking structure introduced. A synergistic effect of interface modifying and silane crosslinking method in improving mechanical performance of the composite is presented. Phase morphology of the LLDPE/Al(OH)₃ composites was studied by means of scanning electron microscopy (SEM) technique. SEM micrographs indicate that a core‐shell type with Al(OH)₃ as a core and EVA as a shell is formed in the composite. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2485–2490, 2002     

Natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) blends

The grafting of the methyl methacrylate (MMA) monomer onto natural rubber using potassium persulfate as an initiator was carried out by emulsion polymerization. The rubber macroradicals reacted with MMA to form graft copolymers. The morphology of grafted natural rubber (GNR) was determined by transmission electron microscopy and it was confirmed that the graft copolymerization was a surface‐controlled process. The effects of the initiator concentration, reaction temperature, monomer concentration, and reaction time on the monomer conversion and grafting efficiency were investigated. The grafting efficiency of the GNR was determined by a solvent‐extraction technique. The natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) (NR‐g‐MMA/PMMA) blends were prepared by a melt‐mixing system. The mechanical properties and the fracture behavior of GNR/PMMA blends were evaluated as a function of the graft copolymer composition and the blend ratio. The tensile strength, tear strength, and hardness increased with an increase in PMMA content. The tensile fracture surface examined by scanning electron microscopy disclosed that the graft copolymer acted as an interfacial agent and gave a good adhesion between the two phases of the compatibilized blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 428–439, 2001     

Thermal Characterization of Upper Critical Solution Temperature m‐LLDPE/Poly(ethylene‐ran‐butene) Elastomer Blends

Summary: The phase and thermal characteristics of blends consisting of linear low‐density polyethylene (LLDPE) (0.7 mol‐% hexene copolymer) and poly(ethylene‐ran‐butene) (PEB) (26 mol‐% butene copolymer) have been investigated using optical microscopy (OM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). An upper critical solution temperature of 162 °C was exhibited. The addition of PEB not only slowed the overall crystallization rate of LLDPE but also changed the distribution of lamellar thickness or perfection of LLDPE crystals. The equilibrium melting temperature of LLDPE in the blends was reduced and kept relatively constant in the bi‐phase state. The blends showed a single‐stage degradation and an intermediate thermal stability between those of the individual components. It could be attributed to their homogeneous states at degradation temperatures and the similar decomposing mechanisms of two components. The kinetic analysis of thermal degradation also confirmed the above results.

Phase diagram of LLDPE/PEB blends.     

Effect of the electron beam irradiation on the properties of epoxidized natural rubber (ENR 50) compatibilized linear low‐density polyethylene/soya powder blends

Linear low‐density polyethylene/soya powder blends were prepared by using an internal mixer at 150°C. The soya powder content ranged from 5 to 40 wt %. Epoxidized natural rubber with 50 mol % epoxidation (ENR 50) was added as a compatibilizer. The blends were irradiated by electron beam (EB) at a constant dose of 30 kGy. The changes in gel fraction, tensile properties, morphological and thermal properties of the samples were investigated. The gel content increased after EB irradiation. However, the increment of gel content was hindered by increasing soya powder content. The tensile strength and Young's modulus of the blends were increased by EB whereas the elongation at break decreased. The tensile fracture surface also support the reduction of elongation at break by EB irradiation. Further analysis on the irradiated blends using Fourier transform infrared spectra indicated an increase of oxygenated product after undergoing EB irradiation. The differential scanning calorimetry result indicated that the melting temperature of the blends decreased after EB irradiation whereas the crystallinity increased. EB irradiation also enhanced the thermal stability of the blends as indicated by thermogravimetric analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical properties of high‐density polyethylene/scrap rubber powder composites modified with ethylene–propylene–diene terpolymer,dicumyl peroxide,and silicone oil

The effect of ethylene–propylene–diene terpolymer (EPDM), dicumyl peroxide (DCP), and dimethyl silicone oil on the mechanical properties of high‐density polyethylene (HDPE) composites filled with 60 mesh cryogenically scrap rubber powder (SRP) was studied. The addition of 10 wt % EPDM, 0.2 wt % DCP, and 4 wt % dimethyl silicone oil significantly increased both the impact strength and elongation at break of the HDPE/SRP composites. After the modification, the impact strength increased by 160%, and the elongation at break increased by 150% for the composites containing 40 wt % SRP. The impact load–time curves showed that the increase of impact energy for the modified composites was attributed to the increase of the maximum force at yield point and the ductile deformation after yielding. The rheological behavior, dynamic mechanical properties, and morphology observation suggested that an enhanced adhesion between SRP and polymer matrix formed in the modified HDPE/SRP composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2020–2027, 2003     

Effect of the compatibilization of linear low‐density polyethylene‐g‐acrylic acid on the morphology and mechanical properties of poly(butylene terephthalate)/linear low‐density polyethylene blends

A poly(butylene terephthalate) (PBT)/linear low‐density polyethylene (LLDPE) alloy was prepared with a reactive extrusion method. For improved compatibility of the blending system, LLDPE grafted with acrylic acid (LLDPE‐g‐AA) by radiation was adopted in place of plain LLDPE. The toughness and extensibility of the PBT/LLDPE‐g‐AA blends, as characterized by the impact strengths and elongations at break, were much improved in comparison with the toughness and extensibility of the PBT/LLDPE blends at the same compositions. However, there was not much difference in their tensile (or flexural) strengths and moduli. Scanning electron microscopy photographs showed that the domains of PBT/LLDPE‐g‐AA were much smaller and their dispersions were more homogeneous than the domains and dispersions of the PBT/LLDPE blends. Compared with the related values of the PBT/LLDPE blends, the contents and melting temperatures of the usual spherulites of PBT in PBT/LLDPE‐g‐AA decreased. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1059–1066, 2002; DOI 10.1002/app.10399     

LLDPE/LDPE/Mg(OH)2/红磷高效阻燃体系的研究

采用线性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)作为阻燃体系的主体，用表面处理过的氢氧化镁(Mg(OH)2)作主阻燃剂，微胶囊化红磷作阻燃增效剂，重点探讨了Mg(OH)2和微胶囊化红磷的阻燃效果。结果表明：Mg(OH)2与红磷并用具有良好的协同效应，是LLDPE／LDPE的高效阻燃体系。     

Nanoscale Cellular Foams from a Poly(propylene)‐Rubber Blend

Plastic foams with nano/micro‐scale cellular structures were prepared from poly(propylene)/thermoplastic polystyrene elastomer (PP/TPS) systems, specifically the copolymer blends PP/hydrogenated polystyrene‐block‐polybutadiene‐block‐polystyrene rubber and PP/hydrogenated polystyrene‐block‐polyisoprene‐block‐polystyrene. These PP/TPS systems have the unique characteristic that the elastomer domain can be highly dispersed and oriented in the machine direction by changing the draw‐down ratio in the extrusion process. A temperature‐quench batch physical foaming method was used to foam these two systems with CO₂. The cell size and location were highly controlled in the dispersed elastomer domains by exploiting the differences in CO₂ solubility, diffusivity, and viscoelasticity between the elastomer domains and the PP matrix. The average cell diameter of the PP/TPS blend foams was controlled to be 200–400 nm on the finest level by manipulating the PP/rubber ratio, the draw‐down ratio of extrusion and the foaming temperature. Furthermore, the cellular structure could be highly oriented in one direction by using the highly‐oriented elastomer domains in the polymer blend morphology as a template for foaming.

     

LLDPE/LDPE/(E/VAC)/Mg(OH)2流变行为的研究

借助HAAKE RHEOCORD90流变仪分别在150，170和190℃下，研究了LLDPE／LDPE／(E／VAC)和LLDPE／LDPE／(E／VAC)／Mg(OH)2体系的流变行为。结果表明：二体系均属非牛顿型假塑性流体。不同剪切速率下，粘流活化能相差很小，说明其熔体粘度对温度均不十分敏感。相同温度下，LLDPE／LDPE／(E／VAC)／Mg(OH)2无卤阻燃复合材料的挤出膨胀比小于LLDPE／LDPE／(E／VAC)，这一特性说明，前者的成型稳定性较后者有所提高。