Degradation of HDPE and LLDPE in closed mixing chamber: a comparison

Summary Two-dimensional NMR and lanthanide shift reagents have been combined for the first time for NMR spectral assignments. The combined approach permitted very detailed interpretation to be made of the one-dimensional ¹H and ¹³C spectra of ethylene-vinyl acetate copolymers.     

Oxidation of polyethylene in closed mixing chamber

The degradation of commercial LDPE was studied under dynamic conditions which simulate the processing. Dynamic oxidation above 140°C is similar to static oxidation under low oxygen pressure both having strong diffusion control. Fragmentation and crosslinking (mainly C? C bonds) compete in the process. The hydroperoxides predominate at the beginning of the mixing. Their quantity rapidly decreases while that of oxo groups increases and becomes predominant. Below 140°C, the conditions are resembling to static oxidation performed under higher oxygen pressure but the process is still somewhat diffusion controlled. The change in the molecular mass is not considerable in the process. The hydroperoxides predominate among the functional groups formed. Their ratio is constant during mixing. The effect of mechanical stress is not considerable. An increase in the mixing speed resulted in an increase in the rate of the processes studied above. The higher the total amount of oxygen incorporated in the PE, the smaller is the remaining oxidative stability.     

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。     

全密度聚乙烯生产工艺现状

概述了全密度聚乙烯的生产工艺,包括气相法的Unipol,Innovene和Spherilene工艺,溶液法的Sclair,Dowlex和Compact工艺,於浆法的Phillips环管工艺。对我国全密度聚乙烯的工业发展提出了建议。     

Weather-Induced Degradation of LLDPE: Calorimetric Analysis

Studies of polymer degradation over the past decade have increasingly been carried out using thermoanalytical methods. These methods involve the measurement of a convenient variable during a gradual, linear increase in temperature. The most widely used of these techniques are thermogravimetry (TG), differential thermal analysis (DTA), and differential scanning calorimetry (DSC). The morphology of a polymer sample (i.e., the crystallinity, shape and size of the crystals, the structure of the surface of the crystals, and the strain of amorphous regions) influences the heat content and its dependence on temperature. The latter can be satisfactorily investigated by calorimetry measurement in a differential scanning calorimeter.     

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。     

Silane grafting reactions of LDPE,HDPE, and LLDPE

Vinyl trimethoxysilane and vinyl triethoxysilane grafting reactions, induced by dicumyl peroxide, of LDPE, HDPE, and LLDPE were investigated. The apparent activation energy of vinyl trimethoxysilane grafting reactions was positive when the reactions were induced by 0.2 phr of the peroxide. The apparent activation energies were negative when 0.05, 0.1, 0.15, and 0.25 phr of peroxide were used. The extents of vinyl trimethoxysilane grafting reactions of polyethylenes were in the order of LLDPE > LDPE > HDPE, although the extents of peroxide cross‐linking were in the order of LDPE > LLDPE > HDPE. As compared with vinyl trimethoxysilane, vinyl triethoxysilane produced a relatively high extent of grafting reactions of LDPE but showed a relatively low rate of water cross‐linking reactions of the silane‐grafted LDPE. The investigation of effects of the amount of peroxide on the vinyl trimethoxysilane grafting reaction heats demonstrated that the extent of silane grafting reactions increased proportionally as peroxide was increased until a certain amount (the value was dependent on the amount of silane used). Beyond this amount of peroxide, the silane grafting did not increase, whereas the peroxide cross‐linking appeared to increase significantly with increasing amounts of peroxide. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3404–3411, 1999     

高密度聚乙烯和线性低密度聚乙烯共混用于包装薄膜的生产

研讨了线性低密度聚乙烯(LLDPE)/高密度聚乙烯(HDPE)共混取代线性低密度聚乙烯(LLDPE)/低密度聚乙烯(LDPE)共混用于包装薄膜的生产,并测试了其物理性能。     

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。     

BHDPE/HDPE/LLDPE共混体系的研究

采用线性低密度聚乙烯(LLDPE)对双峰高密度聚乙烯(BHDPE)和高密度聚乙烯(HDPE)进行共混,测定共混物的力学性能和DSC曲线。结果显示共混物均可以产生共晶,LLDPE对BHDPE力学性能影响较大;在LLDPE/HDPE中添加BHDPE,三者共混物具有更好的力学性能,流变性能显示三者共混物体系黏度变化不大,为制备性能最优、成本最低的三者共混物提供了依据。     

HDPE/LLDPE/OMMT纳米复合材料的结构与性能

采用直接注射法制备HDPE/LLDPE/OMMT纳米复合材料,采用透射电子显微镜研究 HDPE/LLDPE/0MMT纳米复合材料的微观结构,研究有机蒙脱土含量对纳米复合材料性能的影响.透射电子显微镜结果显示,制备的HDPE/LLDPE/OMMT纳米复合材料是一种半剥离型的纳米复合材料.结果表明:蒙脱土的加入大大提高了纳米复合材料的力学性能和热变形温度.当有机蒙脱土质量含量仅为6%时,屈服强度和拉伸模量分别提高14.0%和59.7%,弯曲强度和弯曲模量分别提高了14.2%和60.O%.     

用双毛细管流变仪对 HDPE与LLDPE挤出压力振荡的研究

用RH2000恒速型双毛细管流变仪研究了3种HDPE和3种LLDPE的挤出压力振荡现象。通过压力振荡图、流动曲线和挤出物表观3方面,对两种类型聚乙烯压力振荡的差异进行了分析。发现HDPE的压力振荡很明显,振幅在2~3MPa,而LLDPE的振幅很小,甚至在压力-时间图上看不出来。6种聚合物的流动曲线都发生了断裂。在柱塞下降速度恒定下发生压力振荡时,流速并不恒定,粘界面条件下流速较小,滑界面条件下流速较大,并通过计算获得了3种HDPE发生压力振荡时对应于粘界面与滑界面的流速。HDPE和LLDPE在粘界面条件下挤出物都是鲨鱼皮,而滑界面条件下HDPE的挤出物类似于无规破裂,LLDPE挤出物表观较光滑,且没有鲨鱼皮。     

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.     

LLDPE与HDPE共混耐温性及在食用菌工业中的应用

线性低密度聚乙烯（ＬＬＤＰＥ）与高密度聚乙烯（ＨＤＰＥ）以３０：７０的比例共混制成的菌袋韧性好．在－１０～２０℃范围内可正常使用而不破裂，达到常压灭菌工艺要求。     

硅烷接枝交联HDPE／LLDPE共混物性能研究

采用引发剂过氧化二异丙苯（DCP）、硅烷偶联剂乙烯基三乙氧基硅烷（VTEOS）和催化剂二月桂酸二丁基锡（DBTL）,通过双螺杆挤出机对高密度聚乙烯（HDPE）和线性低密度聚乙烯（LLDPE）的共混物进行硅烷接枝交联反应。通过力学测试和DSC研究产物不同凝胶含量对其性能影响。研究表明硅烷交联聚乙烯的拉伸和冲击强度随交联度的增大而提高,但产物结晶度和熔点有所下降,同时结晶均匀性变差。     

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.     

HDPE/LLDPE/POE薄膜性能的研究

采用线型低密度聚乙烯（LLDPE）和热塑性弹性体乙烯-辛烯共聚物（POE）对高密度聚乙烯（HDPE）薄膜进行改性,研究了LLDPE和POE对共混体系薄膜力学性能、加工性能的影响,探讨了LLDPE增强HDPE的机理。结果表明,加入一定量LLDPE,使HDPE／LLDPE薄膜的拉伸强度较纯HDPE薄膜有所增加,而单位冲击破损质量则有所下降。当w（LLDPE）为15％时,HDPE／LLDPE薄膜的拉伸强度提高21．6％,薄膜的单位冲击破损质量降低23．0％。在HDPE／LLDPE/POE三元体系中,当w（POE）,w（LLDPE）分别为10％,15％时,薄膜的拉伸强度、单位冲击破损质量、断裂伸长率比纯HDPE薄膜分别提高2．3％,113％。36．0％,综合性能良好。     

HDPE/LLDPE共混用于大型注射件生产的研究

探讨了线型低密度聚乙烯(LLDPE)对高密度聚乙烯(HDPE)的改性作用,确认以LLDPE作为改性剂,可有效改善纯HDPE制品的脆性,提高韧性和强度,且能降低能耗,降低制品的原料成本,对大型注射件的生产是个效益显见的尝试.     

Photo‐induced scission and crosslinking in LDPE,LLDPE, and HDPE

The molecular degradation characteristics of three different polyethylenes were determined by deriving chain scission and crosslinking concentrations from gel permeation chromatography molecular weight distributions obtained after 3 weeks and 6 weeks laboratory ultraviolet exposure. Injection‐molded bars (3 mm thick) made from a low‐density polyethylene (LDPE), a linear low‐density polyethylene (LLDPE), and a high‐density polyethylene (HDPE) were used and all showed strong depth variations in degradation. Degradation was rapid near the exposed surfaces but very little change occurred in the bar centers, due to oxygen starvation. The most rapid rises in scission and crosslink concentrations were observed with LDPE, for which the concentrations after 6 weeks exposure were approximately double those measured after 3 weeks. With LLDPE and HDPE the scission and crosslink concentrations after 6 weeks exposure were very much greater than twice those after 3 weeks. Scission dominated over crosslinking at all depths and for all materials the scission/crosslink ratio was always ≥3, with a value of ～9 recorded for HDPE near the exposed surface after 6 weeks exposure. POLYM. ENG. SCI., 45:579–587, 2005. © 2005 Society of Plastics Engineers