聚烯烃共混研究

研究了LLDPE/HDPE、LLDPE/LDPE、HDPE/PP及HDPE/PP/EVA各共混体系的配比对拉伸性能的影响,并利用示差扫描量热计、毛细管流变仪分别对其中某些共混物的相容性及加工性能作了进一步探讨。结果表明,LLDPE/HDPE两组分能以任何配比互混,且配比为30/70时拉伸性能超过了纯组分,加工行为优于LLDPE;LLDPE/LDPE是不相容或存在极限相容性的多相共混物,其拉伸性能没有表现出强烈的协同效应,且配比低于40/60时,拉伸性能低于预料的迭加值;HDPE/PP是相容性很差的共混体系,其拉伸性能低于纯组分,在HDPE/PP共混物中加入EVA(乙烯-醋酸乙烯共聚物)后,其拉伸性能没有得到可望的改善,却降低了低剪切速率时的加工行为。     

硅烷接枝交联LDPE、LLDPE及其共混物的结构研究

利用红外光谱、凝胶渗透色谱、热延伸试验、差示扫描量热法、扫描电子显微镜等方法研究了低密度聚乙烯（LDPE）、线型低密度聚乙烯（LLDPE）及其共混物的乙烯基硅烷接枝及交联产物的分子结构、熔融行为和形态。结果表明：硅烷接枝后，LDPE、LLDPE的重均摩尔质量小幅增加；硅烷接枝交联能力为：LLDPE〉LDPE／LLDPE共混物〉LDPE；接枝和交联使LDPE、LLDPE及其共混物的结晶度降低，晶粒变得不均匀；硅烷接枝和交联能增加LDPE／LLDPE共混物的相容性；交联结构提高了LDPE、LLDPE及其共混物的抗冲性。     

硅烷接枝交联HDPE、LLDPE及其共混物的结构研究

利用红外光谱、差示扫描量热法等方法研究了高密度聚乙烯(HDPE)、线性低密度聚乙烯(LLDPE)及其共混物的乙烯基三乙氧基硅烷(VTEOS)接枝及交联产物的分子结构、熔融行为。结果表明,VTEOS接枝交联PE能力为:LLDPE>HDPE/LLDPE共混物>HDPE;接枝和交联使HDPE、LLDPE及其共混物的结晶度和熔点降低,晶粒变得不均匀。     

硅烷接枝HDPE和LLDPE的反应动力学研究

用差示扫描量热法研究了过氧化二异丙苯引发的硅烷接枝高密度聚乙烯(HDPE)、线型低密度聚乙烯(LLDPE)反应及其动力学特性。结果表明,该反应可按假定的自由基反应机理,用简化的动力学模型描述,遵循一级反应动力学,得出HDPE、LLDPE的接枝反应活化能分别为(190±5)kJ/mol、(160±5)kJ/mol,LLDPE的接枝反应热和反应程度大于HDPE。     

硅烷接枝HDPE/纳米SiO_2复合材料的制备与性能

将经表面处理后的纳米SiO2和硅烷接枝高密度聚乙烯(HDPE)熔融共混制得硅烷接枝HDPE/纳米SiO2复合材料,并对其结晶行为、力学性能及热性能进行了研究。结果表明:与HDPE相比,硅烷接枝HDPE/纳米SiO2复合材料的结晶度降低约17%;在纳米粒子含量为6%时,热分解温度提高了15℃;在纳米粒子含量为10%时,体系的拉伸强度提高了25%。     

LLDPE/HDPE的反应挤出接枝及其热粘合性能

使用反应挤出机研究了线性低密度聚乙烯(LLDPE)和高密度聚乙烯(HDPE)混合物在反应挤出过程中接枝马来酸酐(MAH)的规律和接枝产物的性能.实验结果表明,在LLDPE中加入高于40%的HDPE,可使接枝产物的维卡软化点达到100℃以上的热熔胶产品要求;接枝产物的接枝率和熔体流动速率主要受过氧化二异丙苯(DCP)用量的控制;最佳的生产配方为:LLDPE/HDPE:60/40,MAH=1.5%,DCP=0.04%.经过红外光谱和示差扫描量热谱分析表明,反应挤出得到的接枝产物与国外同类产品的结构与组成相同,产品几乎无刺激性气味;随着接枝产物接枝率的提高,产物对钢板的剥离强度提高.钢板表面涂上环氧树脂后的热熔胶的剥离强度成倍增加.     

聚乙烯反应挤出接枝马来酸酐的研究

以过氧化二异丙苯(DCP)为引发剂,使用反应挤出机研究了不同种类聚乙烯及其共混物接枝马来酸酐的反应规律。实验结果表明:产物的接枝率和熔体流动速率(MFR)变化与聚乙烯的种类有直接关系,接枝性能从优到差的顺序为:LDPE>LLDPE>HDPE;引发剂DCP对LDPE接枝产物的MFR影响显著,对LLDPE次之,对HDPE的MFR几乎没有影响;聚乙烯共混物的接枝性能取决于组成共混物的聚乙烯种类和用量。接枝产物及纯化后样品的红外光谱分析表明,酐基是以化学键连接到聚乙烯分子链上,接枝产物几乎不含游离态的马来酸酐。     

LDPE HDPE LLDPE的硅烷接枝反应

研究了DCP (过氧化异丙苯)为引发剂,A1 71 (乙烯基三甲氧基硅烷)与A1 51 (乙烯基三乙氧基硅烷)在LDPE (低密度聚乙烯) ,HDPE (高密度聚乙烯) ,LLDPE (线性低密度聚乙烯)上的接枝反应。A1 71接枝反应过程中,当过氧化物的加入量为0 .2 %时,活化能为正值。而当加入量为0 . 0 5%、0 . 1 %、0 . 1 5%、0 2 5%时,活化能为负值。尽管过氧化物在PE (聚乙烯)中交联反应程度的顺序为:LDPE >LLDPE >HDPE ,但A1 71接枝反应程度的顺序为LLDPE >LDPE >HDPE。与A1 71相比,A1 51在LDPE上具有较高的接枝反应速率,但它在水交联反应过程中,呈现出相对较低的反应速率。通过研究加入过氧化物量的变化对A1 71接枝反应热的影响,可知在过氧化物未达到一定量前(这个数值取决于所加入的硅烷的量) ,当过氧化物增加时,反应热是随之增加的。     

LLDPE/LDPE共混物的结构与性能

以线型低密度聚乙烯(LLDPE)与低密度聚乙烯(LDPE)为原料,按m(LLDPE)∶m(LDPE)=75∶25共混,经挤出机熔融吹膜制备了LLDPE/LDPE薄膜。采用差示扫描量热仪、凝胶渗透色谱仪、电子万能试验机、雾度仪和旋转流变仪等研究了LLDPE,LDPE,LLDPE/LDPE共混物的结晶行为、流变行为、热性能以及所制薄膜的力学性能、光学性能等,并简要分析了其各项性能得到改善的原因。结果发现:LLDPE/LDPE薄膜具有较好的综合力学性能、光学性能、加工性能。     

铝塑复合管硅烷交联聚乙烯专用料的研究

研究了高密度聚乙烯（HDPE）／线性低密度聚乙烯（LLDPE）硅烷接枝交联体系。分析了过氧化二异丙苯（DCP），乙烯基三乙氧基硅烷（VTES），加工设备及工艺条件（温度，螺杆转速）对体系熔体流动速率（MFR）和凝胶含量的影响。并用Buss混炼设备制备出高流动性的铝塑复合管硅烷接枝交联PE专用料。     

Silane grafting and moisture crosslinking of polyethylene: The effect of molecular structure

The silane grafting and moisture crosslinking of different grades of polyethylene have been investigated. Three types of polyethylene (HDPE, LLDPE, and LDPE) with different molecular structures and similar melt flow indices were selected. The initiator was dicumyl peroxide (DCP), and the silane was vinyltrimethoxysilane. The grafting reaction was carried out in an internal mixer. The extent of grafting and the degree of crosslinking were determined, and hot‐set tests were carried out to evaluate the crosslink structure of the different polyethylenes. The LLDPE had the highest degree of grafting, while the LDPE had the least. The rate of crosslinking for LDPE was higher than that of HDPE and LLDPE. The gel content of LDPE was higher than that of HDPE and LLDPE. Hot‐set elongation and the number‐average molecular weight between crosslinks (M_c) were lower for LLDPE and LDPE than for HDPE. Increasing the silane/DCP percentage led to peroxide crosslinking, thereby decreasing the M_c and hot‐set elongation. The number‐average molecular weight (M_n), molecular weight distribution, and number of chain branches were the most important parameters affecting the silane grafting and moisture crosslinking. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Rheological and mechanical properties in polyethylene blends

Melt rheology and mechanical properties in linear low density polyethylene (LLDPE)/low density polyethylene (LDPE), LLDPE/high density polyethylene (HDPE), and HDPE/LDPE blends were investigated. All three blends were miscible in the melt, but the LLDPE/LDPE and HDPE/LDPE blends exibiled two crystallization and melting temperatures, indicating that those blends phase separated upon cooling from the melt. The melt strength of the blends increased with increasing molecular weight of the LDPE that was used. The mechanical properties of the LLDPE/LDPE blend were higher than claculated from a simple rule of mixtures, whiele those of the LLDPE/HDPE blend conformed to the rule of mixtures, but the properties of HDPE/LDPE were less than the rule of mixtures prediction.     

不同分子链结构聚乙烯的交联研究

研究了线性、短支链和长支链支化三种分子链结构聚乙烯的化学交联过程,对交联体系的机械性能和热性能进行了分析对比。结果表明,在同样交联剂含量情况下,聚乙烯交联体系的凝胶含量顺序是:长支链支化>短支链支化>线性结构;交联引起的拉伸强度变化率为长支链支化>短支链支化>线性结构;交联引起的断裂伸长率变化率为线性结构>短支链支化>长支链支化;交联引起结晶度的下降程度为线性结构>短支链支化>长支链支化。     

Formation and characterization of polyethylene blends for autoclave‐based expanded‐bead foams

Blends of linear‐low‐density polyethylene (LLDPE), low‐density polyethylene (LDPE), and high‐ density polyethylene (HDPE) were foamed and characterized in this research. The goal was to generate clear dual peaks from the expanded polyethylene (EPE) foam beads made from these blends in autoclave processing. Three blends were prepared in a twin‐screw mixing extruder at two rotational speeds of 5 and 50 rpm: Blend1 (LLDPE with 20 wt% HDPE), Blend 2 (LLDPE with 20 wt% LDPE), and Blend 3 (LLDPE with 10 wt% HDPE and 10 wt% LDPE). The differential scanning calorimetric (DSC) measurement was taken at two cooling rates: 5 and 50°C/min. Although no dual peaks were present, the results showed that blending with HDPE has a more noticeable effect on the DSC curve of LLDPE than blending with LDPE. Also, the rotational speed and cooling rate affected the shape of the DSC curves and the percentage area below the onset point. The DSC characterization of the batch foamed blends revealed multiple peaks at certain temperatures, which may be mainly due to the annealing effect during the gas saturation process. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

A molecular dynamics study of the effects of branching characteristics of LDPE on its miscibility with HDPE

The effects of branching characteristics of low-density polyethylene (LDPE) on its melt miscibility with high-density polyethylene (HDPE) were studied using molecular simulation. In particular, molecular dynamics (MD) was applied to compute Hildebrand solubility parameters (δ) of models of HDPE and LDPE with different branch contents at five temperatures that are well above their melting temperatures. Values computed for δ agreed very well with experiment. The Flory-Huggins interaction parameters (χ) for blends of HDPE and different LDPE models were then calculated using the computed δ values. The level of branch content for LDPE above which the blends are immiscible and segregate in the melt was found to be around 30 branches/1000 long chain carbons at the chosen simulation temperatures. This value is significantly lower than that of butene-based linear low-density polyethylene (LLDPE) (40 branches/1000 carbons) in the blends with HDPE computed by one of the authors (polymer 2000; 41:8741). The major difference between LDPE and LLDPE models is that each modeled LDPE molecule has three long chains while each modeled LLDPE molecule had only one long chain. The present results together with those of the LLDPE/HDPE blends suggest that the long chain branching may have significant influence on the miscibility of polyethylene blends at elevated temperatures.     

Cocrystallization and miscibility studies of blends of ultrahigh molecular weight polyethylene with conventional polyethylenes

Ultrahigh molecular weight polyethylene (UHMWPE) was mechanically mixed with conventional polyethylenes (LLDPE, HDPE, and LLDPE) using an internal mixer. Rheological studies of these blends suggest that UHMWPE seems to be miscible with LLDPE, HDPE, and LDPE in the melt state. Yield characteristics are observed in all blend systems, particularly in high UHMWPE blend compositions. Differential scanning calorimetry and small-angle light scattering studies show that cocrystallization takes place in the blends of UHMWPE/LLDPE and UHMWPE/HDPE blends. However, separate crystals are formed in UHMWPE/LDPE. The formation of separate crystals may be attributed to long chain branching of conventional low-density polyethylene. Tensile properties of the former two blends vary almost linearly with blend compositions, while deviations are seen in the latter UHMWPE/LDPE blends.     

Oriented structure and anisotropy properties of polymer blown films: HDPE, LLDPE and LDPE

Different types of polyethylene blown films (HDPE, LDPE, LLDPE) differ significantly in the ratio between machine and transverse direction tear resistance. In this paper, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) blown films at different draw-down ratios are studied, and the relation between crystalline structure and anisotropy of blown film properties is investigated. The crystalline morphology and orientation of HDPE, LDPE, LLDPE blown films were probed using microscopy and infrared trichroism. Significant differences in crystalline morphology were found: at medium DDR HDPE developed a row-nucleated type morphology without lamellar twisting, LDPE showed rod-like crystalline morphology and turned out to the row-nucleated structure with twisted lamellae at high draw-down ratio (DDR), while a spherulite-like superstructure was observed for LLDPEs at all processing conditions. They also showed quite different orientation characteristics corresponding to different morphologies. The morphologies and orientation structure for LDPE, LLDPE and HDPE are related to the stress applied (DDR) and their relaxations in the flow-induced crystallization process, which determine the amount of fibrillar nuclei available at the time of crystallization and therefore, the final crystalline morphology. These structure differences are shown to translate into different ratios of machine and transverse direction tear and tensile strengths.     

Thermal characteristics and temperature profile changes of structurally different polyethylenes with peroxide modifications

Crosslinking and processing characteristics of polyethylenes (PEs) with different molecular architectures, namely high‐density polyethylene (HDPE), linear low‐density polyethylene (LLDPE), and low‐density polyethylene (LDPE), were studied with regard to the effects of peroxide modifications and coolant flow rates. Dicumyl peroxide (DCP) and di‐tert‐butyl peroxide (DTBP) were used as free‐radical inducers for crosslinking the PEs. The characteristics of interest included normalized gel content, real‐time temperature profiles and their cooling rates, exothermic period, crystallinity level, crystallization temperature, and heat distortion temperature. The experiments showed that LDPE exhibited the highest normalized gel content. The real‐time cooling rates, taken from the temperature profiles for all PEs before the crystallization region, were greater than those after the crystallization region. The cooling rate of the PEs increased with the presence of DCP, whereas the crystallization temperature of the PEs was lowered. The HDPE appeared to show the longest exothermic period as compared with those of the LLDPE and LDPE. The exothermic period showed an increase with increasing coolant flow rate, but it was decreased by the use of DCP. As for the effect of peroxide type, the gel content and cooling rate of the PE crosslinked by DCP were higher than those for the PE crosslinked by DTBP. The DTBP was the more effective peroxide for introducing crosslinks and simultaneously maintaining the crystallization behavior of the PE. J. VINYL ADDIT. TECHNOL., 20:80‐90, 2014. © 2014 Society of Plastics Engineers     

Modification of recycled high‐density polyethylene by low‐density and linear‐low‐density polyethylenes

The present study investigated mixed polyolefin compositions with the major component being a post‐consumer, milk bottle grade high‐density polyethylene (HDPE) for use in large‐scale injection moldings. Both rheological and mechanical properties of the developed blends are benchmarked against those shown by a currently used HDPE injection molding grade, in order to find a potential composition for its replacement. Possibility of such replacement via modification of recycled high‐density polyethylene (reHDPE) by low‐density polyethylene (LDPE) and linear‐low‐density polyethylene (LLDPE) is discussed. Overall, mechanical and rheological data showed that LDPE is a better modifier for reHDPE than LLDPE. Mechanical properties of reHDPE/LLDPE blends were lower than additive, thus demonstrating the lack of compatibility between the blend components in the solid state. Mechanical properties of reHDPE/LDPE blends were either equal to or higher than calculated from linear additivity. Capillary rheological measurements showed that values of apparent viscosity for LLDPE blends were very similar to those of the more viscous parent in the blend, whereas apparent viscosities of reHDPE/LDPE blends depended neither on concentration nor on type (viscosity) of LDPE. Further rheological and thermal studies on reHDPE/LDPE blends indicated that the blend constituents were partially miscible in the melt and cocrystallized in the solid state.     

Flow behavior of LDPE and its blends with LLDPE I and II: A comparative study

Studies on melt rheological properties of blends of low density polythylene (LDPE) with selected grades of linear low density polyethylene (LLDPE), which differ widely in their melt flow indices, are reported. The data obtained in a capillary rheometer are presented to describe the effects of blend composition and shear rate on flow behavior index, melt viscosity, and melt elasticity. In general, blending of LLDPE I that has a low melt flow index (2 _g/10 min) with LDPE results in a decrease of its melt viscosity, processing temperature, and the tendency of extrudate distortion, depending on blending ratio. A blending ratio around 20–30% LLDPE I seems optimum from the point of view of desirable improvement in processability behavior. On the other hand, blending of LLDPE II that has a high melt flow index (10_g/10 min) with LDPE offers a distinct advantage in increasing the pseudoplasticity of LDPE/LLDPE II blends. © 1996 John Wiley & Sons, Inc.