超临界水中添加过氧化苯甲酰对聚丙烯降解的促进作用

The effect of benzoyl peroxide （BPO） on polypropylene （PP） degradation in supercritical water was investigated with the aim of developing a process for recycling of waste plastics. A series of experiments with and without BPO were carried out at temperatures of 653 K and 673 K under pressure about 26 MPa for 30, 75 and 120 min respectively. Products were analyzed by an Ostward-type viscometer, gas chromatography and spectrometry （GC/MS） etc. The results indicated that mean molecular weight of the samples decreased greatly along with the time elapsing or with the temperature increasing, and PP was decomposed to Miphatic and cycloparaftinic hydrocarbons but a few benzenoid hydrocarbons. By comparing the experiments with and without BPO, it was made clear that BPO is an effective additive on PP degradation in supercritical water.     

超临界水降解聚丙烯的工艺研究

采用间歇式管式反应器进行了超临界水降解聚丙烯实验,研究了影响聚丙烯降解的因素。实验结果表明,在温度400－450℃、压力23－35MPa及反应时间60－120min的条件下,超临界水能有效地降解聚丙烯。反应温度和反应时间是影响聚丙烯降解的主要因素,温度越高、时间越长,聚丙烯降解越彻底;聚丙烯颗粒度越小降解速率越快,粉末原料在温度400℃、反应时间60min时,以油相产物为主;在温度450℃、反应时间120min时,有利于得到气相产物。     

超临界水降解聚丙烯机理及产物研究

采用间歇式管式反应器进行了超临界水降解聚丙烯实验,对降解产物分别进行了GC-MS检测分析,研究了聚丙烯在超临界水中的降解机理及产物分布.结果表明,采用超临界水可将聚丙烯塑料彻底降解为液态油状物和可燃性气体.芳香烃类化合物和甲烷分别为液态油状物和气相产物中的主要组分;水相中存在少量醇类和酚类物质.聚丙烯在超临界水中的降解是通过自由基反应进行的,链引发主要由·OH自由基完成.     

在超临界水中聚苯乙烯泡沫的降解

本文研究了聚苯乙烯泡沫在超临界水中的降解反应。考查了反应时间、温度和添加剂对降解反应的影响。实验结果显示,超临界水能将聚苯乙烯泡沫降解为油状产物。在反应的前３０ｍｉｎ内,分子量降低了约９８％;提高温度对反应时间短的和／或无添加剂的配方有明显的促降解作用;添加剂用量在５％左右时,可得到更大的效率／成本比。     

在超临界水中聚苯乙烯泡沫的降解

本文研究了聚苯乙烯泡沫在超临界水中的降解反应。考查了反应时间、温度和添加剂对降解反应的影响。实验结果显示,超临界水能将聚苯乙烯泡沫降解为油状产物。在反应的前30min内,分子量降低了约98％;提高温度对反应时间短的和/或无添加剂的配方有明显的促降解作用;添加剂用量在5％左右时,可得到更大的效率/成本比。     

ε-酸在超临界水中的氧化降解

实验研究了典型有机污染物ε -酸在超临界水中的氧化降解.结果表明,超临界水氧化技术能有效地降解废水中的有机污染物,COD去除率可达99%以上.随着反应温度的升高、压力的增大、停留时间的延长和初始废水浓度的增大,COD去除率也随之提高.ε-酸在超临界水中氧化降解的动力学方程为:-d[COD]/dt =9.75104exp(-8.3804/RT)[COD]1.06[O2]00.165     

超临界水降解丁腈橡胶

采用间歇式管式反应器进行了超临界水降解丁腈橡胶实验,研究了影响丁腈橡胶降解的因素.实验结果表明,在压力22.7～33.5MPa、温度400～450℃和反应时间20～120min的条件下,超临界水能有效地降解丁腈橡胶,转化率可达91.25%,最大油化率为63.09%.反应温度和反应时间是影响丁腈橡胶降解的主要因素,温度越高、时间越长丁腈橡胶降解越彻底.当温度为450℃时,反应60min以油相产物为主;反应120min有利于得到气相产物.     

超临界水氧化法降解葡萄糖的研究

实验研究了葡萄糖在超临界水中的氧化降解。结果表明 ,超临界水氧化技术能有效地降解废水中的葡萄糖 ,COD去除率可达 98%。随着反应温度的升高、压力的增大、停留时间的延长和初始废水浓度的增大 ,COD去除率也随之提高。葡萄糖在超临界水中氧化降解的动力学方程为- d[COD]dτ =2 4.2 exp - 3.0× 10 4RT [COD]1.0 3 [O2 ]0 .0 670     

磺酸萘在超临界水中氧化降解路径的研究

采用GC-MS对1-氨基-2-羟基-4-磺酸萘有机污染物在超临界水中氧化降解的产物进行了分析和鉴别,通过对中间产物的鉴别和结合相关研究提出了其在超临界水中氧化降解的路径。1-氨基-2-羟基-4-磺酸萘氧化降解的路径可用纵横交叉模式描述,即纵向的氧化开环降解反应和横向的耦合反应,该污染物及其带芳环中间产物进一步氧化都经过苯酚,并由其继续开环氧化降解。     

PP/超临界CO2连续挤出发泡成型

以超临界CO2为发泡剂,在连续挤出发泡过程中研究了超临界CO2用量对高熔体强度均聚聚丙烯(PP)发泡成型过程的影响.随着超临界CO2用量的增加,发泡挤出机口模压力降低,试样发泡倍率降低,泡孔尺寸变小,泡孔密度提高.在w(CO2)为3%,5%时,得到发泡倍率最高为13左右的PP发泡材料.w(CO2)为7%,发泡温度为12...     

不同粉体对聚丙烯纤维光降解性能的影响

在加速光老化实验条件下,研究超细二氧化钛、超细氧化锌、抗菌沸石(ZA)和乙烯-醋酸乙烯酯共聚物(EVA)对聚丙烯纤维光降解性能的影响。研究发现:超细氧化锌对基体聚丙烯表现出明显的光屏蔽性能,超细二氧化钛表现出光催化活性,ZA和EVA仅作为光惰性填料存在。纤维机械性能的变化可采用指数函数进行拟合,拟合指数越大,材料的耐光老化性能越好。红外分析表明:光降解后纤维体系生成大量的羰基基团,并在红外1700~1 800 cm-1区域出现宽的吸收峰。     

超临界水氧化技术研究及进展

介绍了超临界水的特性 ,并对超临界水氧化技术的研究及应用进行了综述 ,提出了超临界水氧化技术的工程应用开发中存在的问题     

Studies on heterogeneous degradation of polypropylene/talc composite: Effect of iron impurity on the degradation behavior

In this study, an effect of iron oxide (Fe₂O₃) impurity in talc on degradation behavior of polypropylene (PP)/talc composite was studied using a PP/Fe₂O₃ model composite sample. The thermal oxidative degradation was performed at 100°C. Although the degradation of a pure PP sample hardly occurred at such temperature, the existence of Fe₂O₃ induced the PP degradation. The degraded PP part was formed around the Fe₂O₃ grain in the PP/Fe₂O₃ sample. It was found from the optical microscope observation that the degraded PP was able to diffuse only within the PP amorphous part. The analysis of the oxidation distribution on the degraded PP surface was performed employing a scanning electron microscope/electron dispersive spectrometer. The result showed that the PP spots in the vicinity of the Fe₂O₃ grain were unoxidized during the initial degradation process, and the oxidized PP spots were located at around 6 μm distance from the Fe₂O₃ grain. It was concluded that the degradation was initiated microscopically away from the Fe₂O₃ grain so that the Fe₂O₃ had both the abilities to accelerate the decomposition of PP hydroperoxide compounds and to reduce the produced radical species into nonradical products. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

超临界甲苯降解聚苯乙烯反应动力学模型

引言 聚苯乙烯是一种性能优良、应用广泛的通用塑料,且可降解回收苯乙烯单体,因此废聚苯乙烯的回收利用受到广泛关注.但聚苯乙烯热降解高温熔融时黏度很大,造成温度分布不均和局部过热,容易发生二次反应并导致结炭,同时降低了苯乙烯单体收率,因此近年来发展了各种热解技术以抑制结炭、提高苯乙烯收率.超临界降解技术利用超临界流体优异的扩散性能和溶解性能,具有加快聚苯乙烯降解速率,提高反应转化率,抑制结炭等优点[1-4].     

Influence of supercritical CO2 on the interactions between maleated polypropylene and alkyl‐ammonium organoclay

Supercritical carbon dioxide (scCO₂) has been proposed as an effective exfoliating agent for the preparation of polymer‐layered silicate nanocomposites, though there is limited fundamental understanding of this mechanism. This study looks at the interactions of this unique green solvent with three maleated polypropylenes of varying anhydride content and molecular size with an alkyl‐ammonium organoclay. Mixtures of compatibilizers and organoclay were melt‐annealed in a high pressure batch vessel at 200°C and subjected to either a blanket of nitrogen or scCO₂ at a pressure of 9.7 MPa. The structures and properties of these melt‐annealed mixtures were characterized by X‐ray diffraction, transmission electron microscopy, Fourier Transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and contact angle measurement. The results indicate that the plasticizing influence of scCO₂ aided intercalation and exfoliation for intercalants of moderate molecular size and anhydride content which would otherwise have limited diffusion into the clay galleries. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

丙烯超临界聚合中原生晶特征

通过广角X射线衍射(WAXD)对由丙烯超临界聚合和传统本体淤浆法制得的等规聚丙烯原生结晶特征进行了研究,并讨论了聚合工艺、预聚温度、粒径、分子量等对原生晶特征的影响。结果表明,超临界聚合法制备的等规聚丙烯(SC-iPP)呈现出α和γ的混合晶型,而采用传统淤浆法制备的等规聚丙烯(C-iPP)只含有单一α晶型,这是因为超临界的高温高压状态,使得体系传热传质阻力较小,更有利于原生晶型的发展。此外,预聚温度、粒径、分子量等因素也对丙烯超临界聚合所制得的SC-iPP结晶特征有显著影响。     

聚丙烯的热降解和燃烧行为

采用热重分析法对聚丙烯(PP)的热降解行为进行了表征,测定了不同升温速率下PP的热降解过程,得出其热降解活化能为239.58 kJ/mol;用锥形量热仪研究了PP的燃烧行为,随着辐射强度增加,PP的热释放速率增加,质量损失速率加快且分解起始时间提前,热释放总量保持恒定;试样厚度对表征材料的燃烧行为有一定影响。     

Studies of thermal oxidative degradation of polypropylene impact copolymer using the temperature rising elution fractionation method

Thermal oxidative degradation of polypropylene impact copolymer has been studied with its fractions obtained using the temperature rising elution fractionation method. The fractions were analyzed using ¹³C NMR, Fourier transform infrared and differential scanning calorimetry measurements, and the chemical structure, isotacticity, conformation and melting point were investigated. It is found that these fractions are composed of a homopolymer or a polymer blend of polypropylene, polyethylene and ethylene–propylene copolymer. The thermal oxidative degradation of each fraction was carried out at 130 °C, and the degradation progress was estimated by the change of molecular weight distribution (from gel permeation chromatography curves). The rate of degradation is found to be dominated by the content of tertiary C? H bonds (propylene unit) and the existence of 3₁ helix conformation corresponding to a crystalline polypropylene part in each fraction. The latter is more evident leading to the degradation reaction path with a lower activation energy. Copyright © 2007 Society of Chemical Industry