极低密度聚乙烯与其它聚乙烯的共混

从结构角度，用ＤＳＣ，ＷＡＸＤ，ＳＡＸＳ研究了聚乙烯（ＰＥ）家族中极低密度聚乙烯（ＶＬＤＰＥ）与其它ＰＥ的互容性．ＨＤＰＥ／ＶＬＤＰＥ是共晶互容的，以其大量无规部分“溶解”了ＨＤＰＥ的结晶缺陷部分，提高了ＨＤＰＥ的Ｔｃ，Ｔｍ，Ｘｃ，结晶峰半高宽变窄，晶胞参数随组成而有最低值．ＶＬＤＰＥ与ＬＬＤＰＥ结构极为相似，ＤＳＣ及ＷＡＸＤ证明其共混物是共晶相容体系．ＬＤＰＥ／ＶＬＤＰＥ的结晶度符合按组成的计算值，但晶胞参数ａ，ｂ以及晶粒尺寸增大，ＤＳＣ上有分别相应于两组份的两个Ｔｍ；ＶＬＤＰＥ的Ｔｃ，Ｔｍ峰高之和高于按组份的计算值，ＬＤＰＥ的Ｔｍ，Ｔｃ则低于计算值．认为是正如ＬＬＤＰＥ／ＬＤＰＥ，ＬＤＰＥ向充满整个体积的ＶＬＤＰＥ中不断填入，以ＶＬＤＰＥ为晶核而结晶，形成相分离的不相容体系．     

双峰分子量分布聚乙烯的研发进展

聚乙烯是通用合成树脂中应用最广泛的品种,主要用来制造薄膜、电线电缆、注塑品、涂层、纤维、管材等。近年来,我国聚乙烯工业发展迅速,但高品质高附加值的聚乙烯如双峰分子量分布聚乙烯仍无法满足国内不断增长的需求,每年需要大量进口。双峰分子量分布聚乙烯能兼顾材料的加工性能和使用性能,是目前聚烯烃高性能化的一个重要方向。本文介绍了...     

聚乙烯基环己烷-聚乙烯-聚乙烯基环己烷三嵌段共聚物溶液的受限结晶研究

嵌段共聚物由于组分间的化学不相容性而发生微相分离,组装成各种有序的纳米结构,如球、圆柱、层及双连续结构等．半晶型嵌段共聚物由于引入了能结晶的组分,使体系中存在两种相互竞争的过程,即微相分离与结晶,所以能形成更为丰富的有序结构．聚乙烯基环己烷-聚乙烯-聚乙烯基环己烷[Poly(Vinylcyclohexane)-b-poly(ethylene)-b-poly(vinylcyclohexane),     

密度对聚乙烯光氧老化特性的影响研究

利用力学试验、凝胶渗透色谱(GPC)、热重分析法(TG)、差示扫描量热法(DSC)、衰减全反射红外光谱技术(ATR-FTIR)、扫描电子显微镜(SEM)比较研究了不同密度聚乙烯(HDPE、LDPE、LLDPE和MDPE)的光氧老化特性,分析了密度对聚乙烯力学性能、分子量、热稳定性、熔融特性、化学结构和表面微观形貌的影响规律。结果表明LDPE弯曲性能、热分解特征温度和氧化诱导温度下降最明显,且区别主要集中在老化初期。老化24d后,HDPE和LDPE冲击强度均已降低。老化64d后,4种PE相对分子质量均下降,其中LDPE相对重均分子质量下降更强烈。LDPE和LLDPE不饱和度增长最快,四种样品支化度变化无明显区别,LDPE的分子链断链作用和氧化作用最为强烈,羰基指数和羟基指数增长最快,表面破坏更严重,由于支链的存在破坏了聚乙烯分子链的规整性,导致LDPE更容易发生老化。     

茂金属聚乙烯和低密度聚乙烯共混物的流变行为

研究了茂金属催化乙烯丁烯1共聚物mPE和LDPE共混物的流变行为.测定了一系列共混物的稳态剪切粘度和动态粘弹性,用改进Cross模型拟合实验数据.mPE的零切粘度η₀较小,从牛顿型转变为非牛顿型所需的剪切速率较大,转变应力较高,在挤出加工剪切速率范围内熔体粘度高,对剪切敏感性差,这是由于它有较低的重均分子量、窄的分子量分布(M_w/M_n=21)所致.对于对数加和规律,共混物η₀在mPE/LDPE为50/50和25/75时有强烈的正偏差,这是由于共混物自由体积减小所致.共混物的转变应力τ^*和非牛顿指数n随LDPE加入量增大而降低,表明共混物对剪切的敏感性提高,加工性得到改善.G'和G”的一致性说明mPE和LDPE共混是相容的.     

聚乙烯单晶的退火效应

用混合晶红外光谱法和ＳＡＸＳ、ＤＳＣ和ＬＡＭ等方法研究了聚乙烯单晶在７５℃、９０℃和１０５℃退火前后的结构变化，发现在９０℃以下和１０５℃以上退火，遵循不同的退火机制     

聚乙烯/超高分子量聚乙烯共混体系相行为的动态流变学研究

研究了高密度聚乙烯(HDPE)/超高分子量聚乙烯(UHMWPE)、线性低密度聚乙烯(LLDPE)/UHMWPE、低密度聚乙烯(LDPE)/UHMWPE三种共混物的动态流变性能。从弹性模量、复数粘度、特征频率和松弛时间的对数线性加和性、Cole-Cole曲线、Han曲线以及时温等效原理的分析表明LDPE/UHMWPE共混物在熔体状态是相容的,而LLDPE/UHMWPE和HDPE/UHMWPE共混物在熔体状态下发生分相过程。     

不同分子量的高密度聚乙烯与茂金属线型低密度聚乙烯的相容性

采用动态流变学测试和结晶动力学的方法研究了两种分子量的高密度聚乙烯(HDPE)与茂金属线型低密度聚乙烯(m-LLDPE)共混体系的相容性.流变学研究表明,HDPE/m-LLDPE共混物在低ω区域lgG′-lgω关系曲线偏离线性规律,在熔融态为非均相体系.DSC分析发现HDPE/m-LLDPE共混物体系中HDPE的熔点随着m-LLDPE含量的增多而逐渐下降,说明HDPE与m-LLDPE二者具有机械相容性.当HDPE在m-LLDPE的熔体中等温结晶,分子量较高的HDPE结晶速率与纯HDPE相近,m-LLDPE的含量变化对Avrami指数n的影响不大;分子量较低的HDPE指数n和半结晶时间t1/2随m-LLDPE含量的增加逐渐增大,结晶速率随着m-LLDPE含量的增加逐渐下降,表明熔融态的m-LLDPE和HDPE存在着较强的分子间相互作用,二者具有一定的相容性.     

辐照聚乙烯单晶的退火研究

用红外光谱、ＤＳＣ、ＳＡＸＳ和ＷＡＸＤ等方法考察了辐照５ＭＧｙ后的聚乙烯单晶在退火前后的结构变化，对比未辐照样品在同样条件下的变化，提出在９０℃以下和１０５℃聚乙烯有不同的退火机理，辐照引起的交联和晶区结构损伤，限制了退火对晶体结构的改善程度．     

超高分子量聚乙烯的红外光谱的特性研究

研究了超高分子量聚乙烯(M_w>1×10⁵)的红外光谱-温度特性.3条非晶谱带(1368、1352和1304cm^-1)的吸收强度均随温度升高而增大,但都比普通分子量聚乙烯增加的小,尤以高于140℃更甚.分子链中次甲基的近程构象序列分布随温度的变化不受分子量的影响,但旁式构象序列分布则随温度升高而增大.升温和降温过程的红外光谱均表明1352和1304cm^-1两谱带随结晶状态的变化比1368cm^-1更敏感.     

Enhanced Adsorption of Bromoform onto Microplastic Polyethylene Terephthalate Exposed to Ozonation and Chlorination

This paper selected microplastic polyethylene terephthalate (PET), commonly found in water/wastewater plant effluent, to investigate the changes of PET oxidized under ozonation (designated as ozonized PET), followed by sodium hypochlorite oxidation (designated as ozonized-chlorinated PET) and studied their influence on the adsorption of the disinfection by-product bromoform (TBM). Fragmentation and cracks appeared on the oxidized PET surface. As the oxidation degree increased, the contact angle decreased from 137° to 128.90° and 128.50°, suggesting hydrophilicity was enhanced. FTIR and XPS analyses suggested that carbonyl groups increased on the surface of ozonized PET and ozonized-chlorinated PET, while the formation of intermolecular halogen bonds was possible when PET experienced dual oxidation. These physiochemical changes enhanced the adsorption of TBM. The adsorption capacity of TBM followed the order of ozonized-chlorinated PET (2.64 × 10⁻⁶ μg/μg) > ozonized PET (2.58 × 10⁻⁶ μg/μg) > pristine PET (2.43 × 10⁻⁶ μg/μg). The impact of raw water characteristics on the adsorption of TBM onto PETs, such as the pH, and the coexistence of inorganic ions and macromolecules (humic acid, surfactant, and bovine serum albumin) were studied. A different predominant adsorption mechanism between TBM and pristine PET or oxidized PETs was proposed.     

Parametric Study of a Pressure Swing Adsorption Process

The performance of a pressure swing adsorption (PSA) process for production of high purity hydrogen from a binary methane-hydrogen mixture is simulated using a detailed, adiabatic PSA model. An activated carbon is used for selective adsorption of methane over hydrogen. The effects of various independent process variables (feed gas pressure and composition, purge gas pressure and quantity, configuration of process steps) on the key dependent process variables (hydrogen recovery at high purity, hydrogen production capacity) are evaluated. It is demonstrated that many different combinations of PSA process steps, their operating conditions, and the feed gas conditions can be chosen to produce an identical product gas with different hydrogen recovery and productivity.     

Identification of Polyethylene by Differential Scanning Calorimetry: Application to forensic science

A forensic sample consisting of melt-recrystallized polymers that was recovered from the scene of a fire in a factory was identified by differential scanning calorimetry. The factory commonly used two kinds of film sheets, A and B, made by different manufacturers. It was necessary to decide whether the forensic sample related to material A or B. The forensic sample and reference samples of materials A and B were subjected to infrared spectroscopy and pyrolysis gas chromatograph mass spectrometry measurements, which revealed their polyethylene nature. The thermal behaviour of the samples was examined by differential scanning calorimetry (DSC) and they were found to be blends of two kinds of polyethylenes, low-density polyethylene and linear low-density polyethylene. The samples could be identified and distinguished from each other via the DSC measurements.This revised version was published online in November 2005 with corrections to the Cover Date.     

Following the Crystallization Process of Polyethylene Single Chain by Molecular Dynamics: The Role of Lateral Chain Defects

Summary: Langevin molecular dynamics (LMD) simulations have been performed in order to understand the role of the short chain branches (SCB) on the formation of ordered domains by cooling ethylene/α-olefins single chain models. Different long single-chain models (C₂₀₀₀) with 0, 5 and 10 branches each 1000 carbons were selected. The branches were randomly distributed along the backbone chain. Furthermore, C₁ (methyl) and C₄ (butyl) branches were taken into account. These models mimic the molecular architecture of ethylene/1-butene and ethylene/1-hexene random copolymers. The simulations are performed according to the following protocol: 20 random chain conformations for each model were equilibrated at high temperature (T* = 13.3) and then they were cooled in steps of 0.45 until the final temperature (T* = 6.2) by running a total of 35 × 10⁶ LMD steps. The distribution peaks of crystallization for each model were calculated by differentiating the global order parameter with respect to the temperature. The Tc* (crystallization temperature) decrease as the number of branches increases as it is experimentally observed. The formation of order in the copolymers is affected by the type and amount of the SCB in the backbone of the polymer chain. The stem lenght and crystallization fraction (α) were defined using the local-bond order parameter. Both parameters decrease as the number of branches increase. In all cases here shown, the C₄ branches are excluded from the ordered domains. However, we have observed that the methyl branch can be incorporated into the ordered regions. These facts satisfactorily agree with experimental data available in the literature.     

紫外辐照官能化LLDPE及改性尼龙66的研究

尼龙66（PA66）是工程塑料的重要品种之一,具有高强度、耐磨、耐油、自润滑和使用温度范围广等优良特性,广泛应用于机械、汽车、电子电器等行业．但PA66在干态和低温下冲击强度偏低,吸水率大,尺寸稳定性差,使其应用范围受到一定的限制。     

High Melting Point of Linear,Spiral Polyethylene Nanofibers and Polyethylene Microspheres Obtained Through Confined Polymerization by a PPM-Supported Ziegler-Natta Catalyst

In this work, different types of polyethylene (linear, spiral nanofibers and microspheres) were obtained via confined polymerization by a PPM-supported Ziegler-Natta catalyst. Firstly, the Ziegler-Natta catalyst was chemical bonded inside the porous polymer microspheres (PPMs) supports with different pore diameter and supports size through chemical reaction. Then slightly and highly confined polymerization occurred in the PPM-supported Ziegler-Natta catalysts. SEM results illustrated that the slightly confined polymerization was easy to obtain linear and spiral nanofibers, and the nanofibers were observed in polyethylene catalyzed by PPMs-1#/cat and PPMs-2#/cat with low pore diameter (about 23 nm). Furthermore, the highly confined polymerization produced polyethylene microspheres, which obtained through other PPM-supported Ziegler-Natta catalysts with high pore diameter. In addition, high second melting point (T_m2: up to 143.3 °C) is a unique property of the polyethylene obtained by the PPM-supported Ziegler-Natta catalyst after removing the residue through physical treatment. The high T_m2 was ascribed to low surface free energy (σ_e), which was owing to the entanglement of polyethylene polymerized in the PPMs supports with interconnected multi-modal pore structure.     

含噻二唑环的阴离子聚合引发剂在合成双官能团聚氧化乙烯中的应用

以氧化乙烯开环聚合为探针反应,考察了含噻二唑环的新型阴离子聚合引发剂(TDZ-K)的引发活性。反应在非均相中进行,分别用甲醇和甲基丙烯酰氯封端,得含双官能团的氧化乙烯聚合产物,其结构经IR,1H NMR,UV,VPO和GPC表征。加入乙酰丙酮,18-冠-6及PEO作助剂,有助于提高TDZ-K的引发活性。