聚乙烯塑料在连续超临界水反应器中的油化研究

在连续超临界水（SCW）反应器中考察了反应温度、停留时间和反应压力对聚乙烯（PE）降解油化的影响。实验结果表明,在120s、25MPa下,从500℃提高到550℃,液体收率呈现先升后降的趋势,在530℃达到最大值（79%）;在520℃、25MPa下,随停留时间的延长,PE裂解程度加深,产物轻质化程度提高,导致液体收率降低,停留240s时,气体收率达到43%;反应压力对产物收率的影响较小,气、液产物中烯/烷比随反应压力的增加而增大。     

聚乙烯燃烧和阻燃的热分析研究

<正> 聚乙烯是一种极易燃烧的高分子材料,氧指数仅17.6,随着其应用面的拓宽和现代社会对防火要求的提高,聚乙烯的阻燃成了越来越重要的课题。目前,聚乙烯及其共混物的阻燃配方已不计其数,理论探讨也有一些报道,但由于对阻燃效果与阻燃剂的性质之间的内在联系尚缺乏足够的认识,所以阻燃剂的选择仍主要依赖于经验及大量的配方试验,缺少系统有效地选择阻燃剂的方法。     

基于Diels-Alder反应的热可逆交联聚乙烯的合成

分别以Ziegler-Natta催化剂和茂金属催化剂(rac-Et(Ind)_2ZrCl_2)引发乙烯/6-呋喃-1-己烯(FH)共聚合,合成了侧基含有呋喃取代基的聚乙烯。再以1,6-二马来酰亚胺基己烷(BMH)为交联剂,通过Diels-Alder反应制备了交联聚乙烯。利用~1H-NMR、DSC等对乙烯/FH共聚物结构进行了表征,利用FTIR、拉伸测试、蠕变实验等对交联聚乙烯的结构与性能进行测定。结果表明,通过改变马来酰亚胺与呋喃的比例可以调节聚乙烯的交联程度,同时Diels-Alder反应的热可逆性赋予交联聚乙烯重复加工性。     

氯化聚乙烯的热可逆共价交联

采用新型热可逆共价交联剂 ,以溶液反应法使氯化聚乙烯 (CPE)交联制得了凝胶量在 80 %左右的共价交联CPE ,研究了不同牌号CPE、催化剂及其用量、反应温度、反应时间及交联剂用量对CPE交联程度的影响 ,并测定了共价交联CPE的热可逆转化特性     

阻燃聚乙烯的裂解气相色谱研究

选择450、500、550、600、650、700℃等不同裂解温度，保持基本一致的进样量(60士1pg)，采用连续升温和分别升温的方法，对聚乙烯及阻燃聚乙烯进行裂解气相色谱(PyGC)分析，比较其性能的差异以及加有不同量阻燃剂的PE的裂解色谱性能．结果表明Si02含量不同的阻燃聚乙烯有较明显的阻燃性能，其中SiO2添加量为6％时阻燃效果最好,PyGC的分析结果与锥形量热仪(CONE)的实验结果相一致．     

红外光谱法在淀粉/聚乙烯低温热氧降解研究中的应用

共聚物;聚乙烯/淀粉共聚物;红外光谱法在淀粉/聚乙烯低温热氧降解研究中的应用     

聚乙烯树脂的连续自成核与退火热分级实验参数优化及其与逐步结晶热分级对比

以支化聚乙烯树脂为研究对象,研究连续自成核与退火热分级实验中,初始温度点(Ts)、升温降温速率、温度间隔(ΔT)和等温时间等实验参数对分级结果的影响,得到了一系列优化的实验参数或范围,为连续自成核与退火热分级方法的实际应用推广提供参考.并将连续自成核与退火(SSA)和逐步结晶(SC)两种热分级的实验结果进行了比较.     

热拉伸的超高分子量聚乙烯的晶体结构和力学性能

讨论了超高分子量聚乙烯（ＵＨＭＷ－ＰＥ）的熔融一次拉伸和二次拉伸的晶体结构和力学性能．利用ＷＡＸＤ和ＳＡＸＤ测定了拉伸片的晶体取向因子和极图，晶粒尺寸，晶体畸变，长周期等晶体结构．用ＤＳＣ和ＶＥＳ测定热性能和动态力学性能．应力－应变实验测定拉伸片的杨氏模量，断裂强度和伸长．这些实验结果说明ＵＨＭＷ－ＰＥ经二次拉伸能产生正交晶系的伸直链晶体．二次拉伸片由折叠链片晶和伸直链晶体两元结构组成．二次拉伸片的杨氏模量比一次拉伸片有大幅度提高．二次拉伸片的晶体结构和力学性能是在一次拉伸的基础上形成的．     

热致液晶性羟乙基纤维素醋酸酯/聚乙烯共混物的热行为

本文用DSC方法研究了热致液晶性羟乙基纤维素醋酸酯（HECA）与聚乙烯（PE）共混物的相转变过程．结果表明，HECA与PE不相容，但当HECA含量＞50％时，则明显影响PE的结晶过程，使其在冷却过程中出现多重结晶。将共况物在393K退火，可改善PE结晶缺陷；在425K退火，可提高HECA液晶相的取向度。     

聚乙烯高压热解及其反应机理研究

塑料废弃物数量日益增加,实现低能耗、高值化利用是促进塑料废弃物回收利用的关键.在380℃设定温度和(1?5)×105 Pa初始压力条件下分别开展聚乙烯高压热裂解和催化热解实验,记录反应过程温度曲线,分析聚乙烯高压热裂解/催化热解产物分布.研究结果表明,反应过程中反应物相态是影响热解反应历程的重要因素;因反应路径而异,压...     

Investigation of spherical oil agglomeration properties of celestite

In this study, concentration of celestite particles was investigated by using oil agglomeration. For this purpose, effects of operating parameters were investigated, and zeta potential measurements and Fourier transform infrared spectrophotometry (FTIR) analyses have also been carried out. In the experiments, effects of operating parameters such as pH, stirring speed, amount of Na oleate as a anionic type collector and kerosene as a bridging liquid, solid ratio, agglomeration time, collector stirring time, conditioning time, and amount of EDTA were investigated to obtain optimum conditions. Zeta potential measurements were carried out for various pH values and amounts of Na oleate. FTIR analyses were investigated to determine the adsorption type of Na oleate on celestite surface. By evaluation of the experimental results, optimum oil agglomeration conditions of celestite were determined as follows: pH 7, stirring speed 1500 rpm, amount of kerosene 100 l/t, amount of Na oleate 10 kg/t, solid ratio 5 wt%, conditioning time 5 min, collector stirring time 1 min, agglomeration time 5 min, and amount of EDTA 1.0 kg/t. In the optimum conditions, celestite was concentrated with recovery of 89.47 wt%.     

超临界水中聚乙烯油化的研究

采用125mL间歇式高压釜反应器，在超临界水条件下考察了反应温度、反应时间、水/聚乙烯比和水填充率对聚乙烯降解油化的影响。实验结果表明,聚乙烯在超临界水中迅速降解，油收率可达90%以上；随温度从450℃提高到480℃，油收率从91.4％下降到61.7％，气体收率从1.9％提高到27.7％；在450 ℃反应时间从1 min延长到30 min时，油收率略有下降，油品中C7-11组分所占比例增大一倍。水/聚乙烯比和水填充率的增加在一定程度上对聚乙烯的降解起抑制作用。     

Effects of thermal history on enthalpy relaxation

The effects of the thermal history on enthalpy relaxation in polymethylmethacrylate (PMMA) have been studied by differential scanning calorimetry (DSC). The temperature dependence of specific heat capacity in the liquid and glassy states, that of relaxation time and the exponent of the Kohlrausch–Williams–Watts function have been obtained by the measurement of the response of heat flux to the sinusoidal temperature variation. The phenomenological model equation as an extension of linear rheology has been applied to enthalpy relaxation. The evolution of entropy under a given thermal history same as the experiment has been calculated and compared with the DSC results. The calculated results reproduce two peaks of specific heat capacity at lower and higher temperatures in the glass transition region: the former is characteristic of PMMA and the latter is observed in typical glassy polymers.     

Investigation of thermal degradation of polystyrene with the aid of thermal analysis

When the DTA of polystyrene is carried out in air in a platinum sample holder, an anomalously high endothermic effect is observed. This effect was found to be related to gas-phase catalytic styrene oxidation occurring on the surface of both operating and reference platinum sample holders. Methodological recommendations are given concerning the DTA procedure for organic substances, making it possible to avoid this type of anomaly.     

Model for thermal self-ignition of two-phase system in a batch reactor

A mathematical model for thermal self-ignition of a two-phase system with a homogeneous bimolecular exothermic reaction in a batch reactor is proposed. The influence of the volumetric ratio of phases and the specific surface area of exchange interface on the parameters of thermal ignition of the system was studied. The kinetic dependences of reactant concentrations and the reactor heating dynamics were investigated.     

Investigation of racemisation in peptide synthesis within a micro reactor

We demonstrate that peptides derived from alpha-amino acids may be prepared in a micro reactor. The peptides were prepared in 20 min with quantitative conversion, compared to batch reactions which require prolonged reaction times. We illustrate that by using dilute reagent concentrations and short reaction times, less racemisation is observed in micro reactions than in bulk reactions.     

Investigation of the complex thermal behavior of fats

The thermal behavior of three ural fats (displaying very different composition), cocoa butter (CB)², lard, and a stearin obtained from anhydrous milk-fat (AMF) fractionation, were studied by both DSC and X-ray diffraction as a function of temperature (XRDT). To perform temperature explorations between –30C and +80C, at rates identical to those used for DSC and ranging from 0.1 K min^–1 to 10 K min^–1, a new set of X-ray sample-holders, temperature-controlled by Peltier effect, has been developed. It is shown that the three more stable polymorphic forms of CB were easily characterized by either X-ray diffraction or DSC, and existence of two -3L forms was confirmed. On the contrary, the more complex polymorphism of lard and AMF required combined examination by DSC and XRDT and the brightness of the synchrotron source for studies at the highest heating rates. Quantitative analysis of the long spacings of XRDT recordings is invaluable for interpretation of thermal events. For instance, it was found that the simultaneous formation of two polymorphic forms, of apparent long spacing of 34 and 42 å, at the onset of lard crystallization might explain the difficulty of its fractionation.Special thanks to Courtney P. Mudd (NIH, Bethesda) for his pertinent advice on the mounting and use of thermoelectric devices. The study of lard crystallization was initiated by Valerie Portalier and suggested by Jean-Luc Vendeuvre of CTSCCV (Maisons-Alfort). For the AMF part of this study, stearin was fractionated by ADRIA Normandie, while characterization of its thermal properties was performed as part of a research program funded by ARILAIT Recherches and the French Ministry of Research and Technology.     

Investigation of the Belousov-Zhabotinsky reaction by thermal lensing

The supramolecular interaction of rubidate (chemically 2,3-naphthalenedicarboxylic acid, 1,4-dihydroxy-diethyl ester) and beta-cyclodextrin (beta-CD) has been studied by spectrofluorimetry. The influence of temperature on the supramolecular system has also been investigated and the thermodynamic parameters were calculated. The results show that beta-CD reacts with rubidate to form a 1:1 host-guest complex with an apparent association constant of 566+/-23 l mol(-1). It was also demonstrated that the thermodynamics of beta-CD-rubidate complex displayed a compensatory enthalpy-entropy relationship. Based on the significant enhancement of the fluorescence intensity of rubidate produced through complex formation, a spectrofluorimetric method for the determination of rubidate in bulk aqueous solution in the presence of beta-CD was developed. The linear relationship between the fluorescence intensity and rubidate concentration was obtained in the range from 2.7x10(-2) to 3.0 mug ml(-1), with a correlation coefficient of 0.9988. The detection limit was 8.2 ng ml(-1) and the relative standard deviation was 1.6%. There was no interference from the excipients normally used in tablet formulations. The application of the present method to the determination of rubidate in tablets gave satisfactory results and was compared with the reference method.     

Dielectric studies of the effects of thermal history on secondary relaxation in bisphenol-a-polycarbonate

The dielectric permittivity and loss of Bisphenol-A-polycarbonate (PC) was measured over the frequency range 100 Hz to 200 kHz and temperature range 77–383 K. One sub-T_g relaxation peak is observed which rapidly broadens with a decrease in temperature. This is attributed to a progressive separation of the γ and β peaks, which at high temperatures are merged to form one peak of high strength. The strength of the sub-T_g relaxations decreases on physical aging of PC but is increased if the sample is quenched from a temperature above its T_g. Slowly cooled PC has a lower strength of its sub-T_g relaxation than a quenched specimen. The thermal history of PC affects the magnitude of its sub-T_g relaxation.