Comparative study on foaming process of thermoplastic polyester and polyether polyurethane with supercritical CO2 as foaming agent

ABSTRACT

The aim of this study was the comparison of beads foaming process and synergistic effect of foaming process parameters on melting crystalline characteristics between thermoplastic polyester and polyether polyurethane(TPU) via batch process using supercritical CO₂(scCO₂) as blowing agent. Method was based on the generation of expandable TPU foam beads (ETPU) prepared by self-designed autoclave foaming apparatus. The surface morphology, cell structure, and crystalline melting characteristics of the ETPU depending on the processing parameters, such as saturation pressure (P_f), saturation temperature (T_f), and saturation time (t_f), were investigated. Results demonstrated both ETPU exhibited fine closed cell morphology with polygons structure and would induce the disappearance of multiple endothermic peaks during the foam process. As any of those three process parameters increased, the HS content, high crystalline melting and E_r were improved, while with regard to cell structure, P_f demonstrated the opposite effect compared with T_f and t_f. Comparing with polyether TPU, polyester TPU possess a larger cell density and a clear bimodal cell structure could be found under certain condition, while beads foaming process had a greater impact on polyether TPU, which had a low density and the appropriate t_f is 2h.     

烷基糖苷对CO2驱泡沫的影响研究

以起泡体积、半衰期为指标,研究了疏水基链长对烷基糖苷(APG)形成CO_2泡沫的性能。结果表明,APG的疏水链越长泡沫越稳定,APG0814的起泡性能优于其他链长APG。研究了质量浓度对APG0814泡沫性能的影响,当APG0814的质量浓度为3 g/L时,形成的CO_2泡沫最稳定;质量浓度越高,起泡体积越大。通过物理模拟实验研究了气液比、实验压强对APG0814形成的CO_2泡沫降低气、水流度的影响,结果表明,气液比为2∶1时,CO_2、水流度降低幅度最大;实验压强越高,CO_2、水流度降低幅度越大。     

Effects of the properties of blowing agents on the processing and performance of extruded starch acetate

The extrusion of polysaccharide‐based polymers, such as starch acetate, is quite different from that of ordinary synthetic polymers. To understand how the physiochemical properties of blowing agents affect plasticization and expansion processes, starch acetate was extruded with water, ethanol, and ethyl acetate. The studied properties and factors were the evaporation rate, surface tension, boiling point, solubility index, latent heat of vaporization of blowing agents, extrusion temperature, and nucleating‐ and blowing‐agent concentrations. The properties of the blowing agents and operating conditions affected the solubility of the matrix polymer, the nucleation process, and cell growth, which affected the foam density and specific volume. A high temperature increased the cell density and specific volume when water and ethanol were used because a high temperature increased the solubility of starch acetate in water and ethanol and promoted nucleation. Ethyl acetate already had high solvency to starch acetate and a high evaporation rate. A high temperature reduced the melting strength, thereby reducing the cell density and specific volume. Water evaporation was greater, despite a high latent heat of evaporation (hr) and boiling point, than the average volumes of ethanol and ethyl acetate that evaporated. The blowing‐agent efficiency was a function of the solvency, blowing‐agent evaporation rate, and operating conditions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1880–1890, 2005     

基于醇胺固定-释放二氧化碳原理的聚氨酯泡沫绿色制备

通过二乙醇胺（DEA）和二氧化碳反应制得一种氨基甲酸铵化合物（DEAC）。DEAC初始分解温度约为54℃,二氧化碳含量14.6%。将不同份数的DEAC作为反应型发泡剂添加到硬质聚氨酯发泡体系中制备泡沫材料,得到密度为90~150 kg·m^-3,压缩强度为0.02~1.65 MPa性能良好的泡沫材料。DEA在火力发电厂作为二氧化碳吸收剂以减少二氧化碳排放。因此,DEAC可以来源于火力发电厂的副产物,成本低廉。本研究为硬质聚氨酯泡沫的制备提供了一种新型的绿色、环保、经济的方法。     

热塑性聚醚酯弹性体硬段含量对其超临界CO 2发泡行为的影响

研究了以聚对苯二甲酸丙二醇酯(PBT)为硬段,聚四氢呋喃醚(PTMG)为软段的热塑性聚醚酯弹性体（TPEE）在超临界CO ₂作用下的固态发泡行为,考察了硬段含量的差异对结晶行为,CO ₂在TPEE中溶解度及扩散行为,以及固态发泡行为的影响。发现硬段含量的差异对TPEE结晶行为影响尤为显著,当硬段含量由29%上升到65%时,其熔点从162.6℃上升至201.9℃,且结晶度由20%上升到40%。结晶的存在抑制了CO ₂在基体内的溶解度且阻碍了其在基体内的扩散。由不同硬段的TPEE中CO ₂溶解度和扩散过程的变化可知,CO ₂更倾向于溶解在TPEE软区内,而由结晶为主构成的硬区中CO ₂溶解量较低。通过研究高压CO ₂环境下的TPEE等温结晶过程发现,经扩散进入TPEE软区内的CO ₂可以提升TPEE链段运动能力,诱导未结晶链段通过规整堆叠而结晶。在CO ₂压力15 MPa经快速降压发泡聚醚酯弹性体,发现随着硬段含量的增加,其温度发泡窗口向高温区移动,当硬段含量为29%时,发泡温度区间为50~160℃,平均孔径4.6~16.5 μm,泡孔密度8.1×10 ⁷~7.5×10 ⁸cells/cm ³,发泡倍率1.1~5.8;当硬段含量为65%时,发泡温度区间为165~195 ℃,平均孔径1.8~6.8 μm,泡孔密度2.6×10 ⁸~1.1×10 ¹¹ cells/cm ³,发泡倍率1.0~4.2。     

Modeling flow and cell formation in foam sheet extrusion of polystyrene with CO2 and co-blowing agents. Part I: Material model

In foam extrusion, process parameters, material properties, and the blowing agent have an influence on the resulting foam properties. For safety and environmental reasons, carbon dioxide (CO₂) has gained importance as a physical blowing agent for the production of low-density polystyrene foam sheets. The sole use of CO₂ often leads to corrugation, open cell structures, or surface defects on the foam sheet. As an alternative, blowing agent mixtures based on CO₂ and organic solvents such as ethanol, acetone, or ethyl acetate can be used, changing solubility and flow behavior of the gas-loaded melt. Modeling of the foaming process in the extrusion die could help to reduce experimental effort and accelerate the development of novel blowing agent mixtures. A model approach to describe the melt behavior of polystyrene loaded with various blowing agent mixtures in the extrusion die is developed. Part I of the article describes the modeling of material properties, that is, rheological behavior by a Carreau-WLF approach with shift factors for temperature, pressure, and blowing agent effects on the glass transition temperature. Solubility behavior is modeled by a combined Henry solubility coefficient approach, showing good agreement with experimental data. Based on the material model, a process model is developed in Part II of this work.     

改性活性炭吸附脱除二氧化碳中微量乙烷

我国对食品级二氧化碳要求较高,在其生产过程中乙烷的脱除是难点。文章首先考察了市售的不同吸附剂,包括Y型、X型、A型等分子筛类,椰壳和煤基活性炭以及吸附树脂等吸附剂对CO2中微量C2H6的吸附效果,之后考察了不同浓度盐酸酸改性与氢氧化钠碱改性、双氧水氧化改性、氨水还原改性等改性条件对吸附剂吸附性能的影响。研究表明,具有高比表面积、丰富微孔和适量中孔结构的活性炭更有益于二氧化碳中微量乙烷的吸附;浓度为1%的盐酸溶液浸渍活性炭3 h后,能增强其对CO2中微量C2H6的吸附能力;浓度3%、浸渍时间6 h为氢氧化钠碱溶液改性活性炭的最佳条件;弱氧化剂双氧水改性能略微提高活性炭对二氧化碳中乙烷的吸附能力,弱还原剂氨水改性对吸附效果无明显影响。     

Modeling flow and cell formation in foam sheet extrusion of polystyrene with CO2 and co-blowing agents. Part II: Process model

In foam extrusion, process parameters, material properties, and the blowing agent have an influence on the resulting foam properties. For safety and environmental reasons, carbon dioxide (CO₂) has gained importance as physical blowing agent for the production of low-density polystyrene foam sheets. The sole use of CO₂ often leads to corrugation, open cell structures, or surface defects on the foam sheet. As an alternative, blowing agent mixtures based on CO₂ and organic solvents such as ethanol, acetone, or ethyl acetate can be used, changing solubility and flow behavior of the gas-loaded melt. A model approach for describing foam extrusion of polystyrene with various blowing agent mixtures in an annular gap die is developed. Part I of the paper describes the modeling of material properties. In Part II, the process model including nucleation and cell formation in the flow field is developed and applied to a foam sheet extrusion process. Based on the material model, melt flow and formation of cells are modeled by a step-wise calculation along the die, showing good agreement with experimental data. Dimensionless numbers are used to describe the foaming process and a parameter study based on these dimensionless numbers is presented.     

Novel injection molding foaming approaches using gas‐laden pellets with N2, CO2, and N2 + CO2 as the blowing agents

A novel method of producing injection molded parts with a foamed structure has been developed. It has been named supercritical fluid‐laden pellet injection molding foaming technology (SIFT). Compared with conventional microcellular foaming technologies, it lowers equipment costs without sacrificing the production rate, making it a good candidate for mass producing foamed injection molded parts. Both N₂ and CO₂ can be suitably used in this process as the physical blowing agent. However, due to their distinct physical properties, it is necessary to understand the influence of their differences over the process and the outcomes. Comparisons were made in this study between using CO₂ and N₂ as the blowing agents in terms of the part morphologies, as well as the shelf life and gas desorption process of the gas‐laden pellets. After gaining a good understanding of the SIFT process and the gas‐laden pellets, a novel foam injection molding approach combining the SIFT process with microcellular injection molding was proposed in this study. Both N₂ and CO₂ can be introduced into the same foaming process as the coblowing agents in a two‐step manner. Using an optimal content ratio for the blowing agents, as well as the proper sequence of introducing the gases, foamed parts with a much better morphology can be produced by taking advantage of the benefits of both blowing agents. In this study, the theoretical background is discussed and experimental results show that this combined approach leads to significant improvements in foam cell morphology for low density polyethylene, polypropylene, and high impact polystyrene using two different mold geometries. POLYM. ENG. SCI., 54:899–913, 2014. © 2013 Society of Plastics Engineers     

超临界二氧化碳对聚合物的增塑作用及应用

简要介绍了超临界二氧化碳的性质及其与聚合物的相互作用 ,着重论述了超临界二氧化碳对聚合物的增塑作用及应用 ,包括小分子渗透、溶胀聚合、抽提分级、聚合物脱挥及微孔材料的制备等     

Investigation of the nanocellular foaming of polystyrene in supercritical CO2 by adding a CO2‐philic perfluorinated block copolymer

Nanocellular foaming of polystyrene (PS) and a polystyrene copolymer (PS‐b‐PFDA) with fluorinated block (1,1,2,2‐tetrahydroperfluorodecyl acrylate block, PFDA) was studied in supercritical CO₂ (scCO₂) via a one‐step foaming batch process. Atom Transfer Radical Polymerization (ATRP) was used to synthesize all the polymers. Neat PS and PS‐b‐PFDA copolymer samples were produced by extrusion and solid thick plaques were shaped in a hot‐press, and then subsequently foamed in a single‐step foaming process using scCO₂ to analyze the effect of the addition of the fluorinated block copolymer in the foaming behaviour of neat PS. Samples were saturated under high pressures of CO₂ (30 MPa) at low temperatures (e.g., 0°C) followed by a depressurization at a rate of 5 MPa/min. Foamed materials of neat PS and PS‐b‐PFDA copolymer were produced in the same conditions showing that the presence of high CO₂‐philic perfluoro blocks, in the form of submicrometric separated domains in the PS matrix, acts as nucleating agents during the foaming process. The preponderance of the fluorinated blocks in the foaming behavior is evidenced, leading to PS‐b‐PFDA nanocellular foams with cell sizes in the order of 100 nm, and bulk densities about 0.7 g/cm³. The use of fluorinated blocks improve drastically the foam morphology, leading to ultramicro cellular and possibly nanocellular foams with a great homogeneity of the porous structure directly related to the dispersion of highly CO₂‐philic fluorinated blocks in the PS matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The synergy of supercritical CO2 and supercritical N2 in foaming of polystyrene for cell nucleation

This study examines the foaming behaviour of polystyrene (PS) blown with supercritical CO₂–N₂ blends. This is achieved by observing their foaming processes in situ using a visualization system within a high-temperature/high-pressure view-cell. Through analyzing the cell nucleation and growth processes, the foaming mechanisms of PS blown with supercritical CO₂–N₂ blends have been studied. It was observed that the 75% CO₂–25% N₂ blend yielded the highest cell densities over a wide processing temperature window, which indicates the high nucleating power of supercritical N₂ and the high foam expanding ability of supercritical CO₂ would produce synergistic effects with that ratio in batch foaming. Also, the presence of supercritical CO₂ increased the solubility of supercritical N₂ in PS, so the concentration of dissolved supercritical N₂ was higher than the prediction by the simple mixing rule. The additional supercritical N₂ further increased the cell nucleation performance. These results provide valuable directions to identify the optimal supercritical CO₂–N₂ composition for the foaming of PS to replace the hazardous blowing agents which are commonly used despite their high flammability or ozone depleting characteristics.     

工业废液吸收低浓度CO2：可行性及应用

化工燃料在提供能源过程中产生的低浓度CO₂废气可以被工业废液吸收。结合当前研究现状,介绍了用工业废液吸收低浓度CO₂废气的研究进展,并开展了可行性分析;归纳了CO₂废气与工业废液的反应原理,将其大致分为中和反应、复分解反应、微生物转化等反应类型,并讨论了其吸收动力学;总结了工业废液吸收低浓度CO₂废气的工艺装置与流程。在废液吸收废气的处理模式中,CO₂的吸收对降低碱液的pH、脱除废液中有害物质效果良好,同时还可以副产微纳米碳酸钙、生物柴油等高附加值产品,实现废弃资源的深度循环利用。此外,分析了工业废液吸收CO₂废气的生命周期评价,通过对能耗、碳排放和成本评估,进一步讨论了工业废液吸收CO₂废气对环境的影响及经济可行性。结合CO₂减排的前景,从工业应用的角度探讨了工业废液用作低浓度CO₂吸收剂面临的挑战,并对其未来产业化发展进行了展望。     

酸改性CoPd/TiO2催化CH4-CO2直接合成C2含氧化合物

采用酸处理方法对CoPd/TiO₂催化剂进行改性,并将酸改性催化剂用于温和条件下CH₄-CO₂梯阶转化直接合成C₂含氧化合物（乙酸和乙醇）的反应。在150～300℃考察了浸酸方式和不同种类酸处理对催化剂活性和选择性的影响。采用X射线衍射（XRD）、X射线光电子能谱（XPS）、NH₃程序升温脱附（NH₃-TPD）和N₂吸附对催化剂进行了表征。结果表明,酸改性明显提高了CoPd/TiO₂上C₂含氧化合物的生成速率和选择性。浸酸方式对催化剂性能和结构有显著影响,先用酸浸渍载体然后再浸渍活性金属所得催化剂具有更高的活性。在H₃PO₄、HNO₃和HCl中,H₃PO₄浸渍的催化剂活性最佳,在150℃时C₂含氧化合物（乙酸和乙醇）的生成速率为3365 μg/(g·h),选择性达到91%。     

中国挤出聚苯乙烯（XPS）泡沫行业CO2混合发泡技术安全生产规范

简单介绍了二氧化碳（CO₂）混合发泡技术制备挤出聚苯乙烯泡沫塑料（XPS）的生产工艺,通过生产安全性分析,详细阐述了发泡剂储存区和高压泵房的安全隐患,分析了XPS泡沫生产过程中易燃发泡剂的可能释放部位和释放几率,并给出了发泡剂储存区、高压泵房和生产车间的安全保障措施,主要涉及到可燃气体探测系统、通排风系统、消防系统、防静电系统的安装要求。     

Improving the Flame Retardancy and Smoke Suppression Properties of Polyurethane Foams with SiO2 Microcapsule and its Flame-Retardant Mechanism

An efficient silicon dioxide (SiO₂) microcapsule was synthesized and used for flame-retardant polyurethane foams. The polyurethane/25?wt% SiO₂ microcapsule composites achieved a limiting oxygen index value of 34.8% and UL-94?V-0 rating, and SDR was significantly reduced. TG, Py-gas chromatography–mass spectrometry, energy dispersive X-ray, and Fourier Transform infrared spectroscopy (FTIP) results indicated that SiO₂ microcapsule could serve as an outstanding flame retardant that operates by both chemical (condensation) and physical (cooling and blocking) mechanisms. The compact and stable char layer formed at the inner layer of the residue during thermal decomposition, and this situation results in the excellent flame retardancy of polyurethane.     

纳米CeO_2催化CO_2与甲醇反应合成碳酸二甲酯的研究

本文介绍了金属催化剂纳米CeO2的制备方法,通过对催化剂结构、性质的表征和催化活性的比较,确定出高效的催化剂,并优化了气固相CO2与甲醇直接合成DMC的反应条件。借此,实验得到以下结果:通过对5种方法制备的纳米CeO2催化剂的比较,发现溶胶凝胶法制备的纳米CeO2催化活性最好,甲醇的转化率可达0.215%,DMC选择性为100%。考察了CO2和甲醇合成DMC的较合适的工艺条件是:反应温度433K,反应压力1.0MPa,催化剂用量0.5g,CO2和甲醇摩尔比2.0,甲醇的转化率可达0.215%,DMC选择性为100%。     

Calculation of the limit pore ranges of the reaction of porous carbon materials with CO2

In the production of activated carbon materials reaction temperature is important for the course of the chemical reaction. The higher the reaction temperature the faster the increase of the reaction rate as against the diffusion rate. In the range of small carbon burn-off reactions the decrease in k_meff values can be ascribed to a reduction of the surface area available for the reaction. Depending on the pore size distribution the surface area can be determined from the walls of the cylindrical tubes. With the help of the pore efficiency value determined from the k_meff values, the limit pore ranges for C0₂ diffusion can be calculated.     

微波辐射烟杆CO2活化制取活性炭及孔结构表征

以烟杆为原料,CO2为活化剂,采用微波辐射法制备了活性炭。采用正交实验研究了CO2流量、活化时间和微波功率对活性炭得率和吸附性能的影响,得到了最佳工艺条件。该工艺将常规加热方法的炭化和活化简化为一个过程,产品的碘吸附值超过了国家一级品标准,所需要加热时间仅为传统法的1/10,同时测定了该活性炭的氮吸附等温线,并通过BET、H-K方程和密度函数理论表征了活性炭的孔结构,结果表明该活性炭为微孔孔型,最后采用电子探针和透射电镜分析了活性炭的微观结构,结果与氮吸附测定的较为一致。     

CO2/N2 separation ability and structural characteristics of poly(butadiene‐co‐acrylonitrile)‐based polyurethanes and hydrogenated nitrile rubbers

Two families of rubbery polymers, commercial hydrogenated nitrile rubbers and synthesized poly(acrylonitrile‐co‐butadiene)‐based polyurethanes with different amount of nitrile groups were studied as CO₂ selective membrane materials. The polymers were characterized by the techniques of FTIR, gel permeation chromatography, WAXD, and differential scanning calorimetry. The permeabilities of pure CO₂ and N₂ were measured using constant pressure/variable volume method at a feed pressure of 6 atm. With a higher amount of polar nitrile group within a given family of polymers, the permeability coefficient (P) was found to decrease, while the permselectivity (α) of these membranes was found to increase. The trade‐off between both transport parameters was less severe for the polyurethanes, which also showed much higher permeabilites. The results obtained were also discussed with respect to the polymer structure, and some relationships were found between P and T_g values. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011