基于熔融接枝烷基链提升聚丁烯发泡行为研究

聚烯烃材料引入长支化结构,能够提升材料熔体强度和异相成核作用,使聚合物具备更加优异的发泡性能,从而扩宽材料的应用领域.本文利用甲基丙烯酸十八烷基酯(SMA)熔融改性聚丁烯(PB),发现其链段缠结程度提升,发泡行为改善.通过红外谱图的化学结构分析以及材料的力学性能分析,发现随着SMA添加量的增加,材料拉伸强度降低,冲击强度呈现先升高后降低的趋势.示差扫描量热(DSC)的分析结果表明改性PB的结晶度下降.采用间歇釜式法制备PB发泡珠粒,利用扫描电子显微镜(SEM)研究发泡珠粒泡孔结构,结果表明：SMA改性后,发泡珠粒平均泡孔尺寸、孔径分布、泡孔密度都得到改善,发泡温度窗口加宽且发泡稳定性提升.当添加SMA达到3份时,珠粒平均泡孔直径为12.3μm,泡孔密度可达38×10~7个/cm~3,发泡倍率接近12倍,其中泡孔密度和发泡倍率分别是纯PB发泡珠粒的9.2倍和1.6倍.本文的研究成果为PB作为发泡材料奠定了工业化基础.     

应用超临界CO2制备微孔聚丙烯的微孔形貌

研究了应用超临界CO2技术制备微孔聚丙烯时发泡条件和聚丙烯(PP)的熔体强度对微孔形貌的影响。结果表明:在一定的饱和压力下,随着温度的升高,PP的变形能力改善,有利于泡孔的长大。随着饱和压力的增加,PP的熔点降低,升高压力和升高温度具有一定的等同作用。由于CO2在PP内分散的不同,高压低温时得到的泡孔比高温低压时得到的泡孔要规整。降压速率对泡孔形貌的影响因饱和压力的大小而异,饱和压力较高时随着降压速率的提高,孔密度增加,泡孔形貌经历了一个从球体到多面体转变的过程。由于PP熔体强度较低,在发泡温度和PP熔点之间非常接近时,CO2气体容易冲破孔壁而使泡孔呈开孔结构。     

提高聚丙烯熔体强度的研究进展

熔融状态下聚丙烯的熔体强度对其发泡效果有着举足轻重的作用,高熔体强度有利于聚丙烯的热成型,从而得到优质的发泡材料。本文综述了聚丙烯泡沫塑料的特点、性能及聚丙烯熔体强度较低对发泡过程的影响,分别从共混改性法、交联改性法、填充改性法这三种提高聚丙烯发泡性能的途径上对目前国内外致力于聚丙烯熔体强度的研究进展进行了重点介绍,指出聚丙烯化学交联改性与共混改性、共聚改性等方法并用乃是改善聚丙烯发泡性能的重点及热点。     

聚丙烯/无机纳米粒子复合材料的发泡行为

利用型腔体积可控注塑发泡装备制备聚丙烯/无机纳米粒子微发泡复合材料,通过复合材料的流变行为和结晶行为,分析了无机纳米粒子对聚丙烯发泡行为的影响。结果表明:无机纳米粒子有促进气泡异相成核作用,同时无机纳米粒子引入可以提高聚丙烯黏弹响应和降温结晶起始温度,起到了抑制泡孔结构恶化的作用,显著改善了聚丙烯的泡孔结构;在聚丙烯材料中添加纳米CaCO3、纳米OMMT、纳米SiO2进行发泡,以PP/OMMT发泡材料的发泡质量最理想,其泡孔密度和尺寸分别为2×106个/cm3和24.2μm。     

热塑弹性体超临界流体间歇发泡过程中的基本问题

超临界流体间歇发泡的体系黏弹性易于调节、加工参数易于控制、加工装备便于设计和实现,是热塑弹性体物理发泡领域中最受关注的技术路线.本文首先综述了热塑弹性体物理发泡相关文献、研发历程和应用现状;阐明间歇发泡技术的相关概念、技术特点以及热塑弹性体与超临界流体的相互作用,重点讨论热塑弹性体间歇发泡的“高弹态发泡”特征以及处于高弹态状态下的泡孔成核、泡孔生长、泡孔结构定型、泡沫收缩机制及其调控策略.其次,综述了热塑弹性体发泡薄膜的制备方法、热塑弹性体发泡珠粒水蒸气成型过程、珠粒界面黏结强度和分子链界面扩散机制.此外,还从分子链化学结构、泡孔结构、材料宏观结构等角度总结了热塑弹性体发泡材料弹性性能,揭示热塑弹性体发泡材料的结构—弹性性能关系.最后对热塑弹性体超临界流体间歇发泡技术进行了展望.     

尼龙6微孔发泡材料的制备及泡孔形貌调控

本文利用共混改性方法得到高熔体强度尼龙6基体,通过探索不同的工艺条件,获得不同倍率的尼龙6发泡材料,系统研究不同离聚体改性剂比例下对其熔体强度的影响.通过热性能测试和流变测试推测了其中微交联结构的存在.通过调节发泡工艺制备不同发泡倍率的尼龙6发泡材料,用扫描电镜(SEM)观测泡孔形貌.结果 表明,离聚体的加入大大提升尼龙6基体的熔体强度,实现了尼龙6超临界二氧化碳发泡的可能性,并获得了较大倍率的尼龙发泡材料.     

PP/HDPE 共混物及其纳米复合材料超临界流体微孔发泡

通过间歇法制备了聚丙烯(PP)/高密度聚乙烯(HDPE)共混物及其纳米复合材料的微孔塑料.用扫描电镜对发泡样品的泡孔结构进行表征,研究了纳米粒子的类型和含量对泡孔结构的影响.结果表明:在PP中加入25%的HDPE可改善泡孔结构;在 PP/HDPE 共混物中加入纳米粒子可使泡孔的直径减小、密度增加、泡孔分布更均匀;泡孔直径随着纳米粒子含量的增加会出现先减小后增加的趋势.     

高熔体强度聚丙烯的制备与表征*

高熔体强度聚丙烯（HMSPP）相比于普通聚丙烯具有优越的综合性能,其良好的加工性能使其具有广阔的应用前景,并成为许多国家近年来竞相开发的热点。本文从HMSPP的结构特点、制备方法、性能测试等方面总结了近年来的研究进展,着重介绍了反应器合成长链支化型高熔体强度聚丙烯（LCB-HMSPP）的方法以及其结构表征,并在总结国内外现状的基础上展望了高熔体强度聚丙烯的发展前景。     

二氧化碳气体制备层状聚苯乙烯发泡材料

将珠状和粒状聚苯乙烯(PS)样品模压后在高压CO₂条件下饱和, 采取快速升温法制备了结构新颖的层状发泡材料. 通过扫描电子显微镜(SEM)以及不同饱和条件下CO₂在PS中溶解度的分析, 初步研究了区域性弱链段缠结力对气体成核、泡孔形态、泡孔尺寸和分布的影响. 结果表明珠状PS在压制成型过程中其珠粒界面链段相互作用力较弱. 由于基体中界面区域链段的缠结能力不同, 在不同区域CO₂气体的成核和增长也不同, 通过控制发泡的过程参数, 可以得到独特的PS层状泡孔形态.     

高分子量级分含量对熔体挤出拉伸法制备聚丙烯微孔膜的影响

通过熔体挤出拉伸法以两种聚丙烯为原料制备微孔膜.通过考察原料分子量数据发现高分子量聚丙烯(PPH)在高分子量级分(重均分子量>106)含量上大于低分子量聚丙烯(F401).PPH的弛豫时间在相同条件下也远大于F401.红外二向光法结果表明,PPH在相同熔体牵伸比下片晶取向度较F401高.相同加工条件下PPH微孔膜片较F401成孔分布更均匀,孔径尺寸也更均匀.2种微孔膜孔隙率都随熔体牵伸比的增加而提高,微孔分布随着熔体牵伸比的提高和片晶取向度的增加而趋于均匀,孔尺寸也随之区域均匀.研究表明,聚合物树脂中高分子量级分含量是影响预制膜中片晶取向度、冷热拉伸成孔分布和尺寸均匀度的重要影响因素.     

Review on the production process and uses of controlled rheology polypropylene—Gamma radiation versus electron beam processing

Controlled rheology polypropylene grades are established commodities in the polymer processing market. However, new types, mainly the so-called high melt strength polypropylene (HMSPP) grades, are being introduced in the last two decades and radiation processing has played an important role. The melt strength properties of a polymer increases with molecular weight and with long-chain branching due to the increase in the entanglement level. As polypropylene (PP) is a linear polymer, the way to improve its elongational viscosity is by the production of a bi-modal polymer. Basell's patents claim the production of long-chain branching on PP by irradiating with electrons under oxygen free atmosphere, followed by two heating steps to allow radical recombination and annihilation reaction. Some other companies have issued patents using electron beam processing, but so far there is no actual production other than the Basell one. As a result of a research joint effort, IPEN, BRASKEM (the biggest Brazilian polymer producer) and EMBRARAD (the major Brazilian radiation processing center) developed a new process to produce HMSPP based on gamma processing. This paper will address some characteristics of each technology and the main industrial opportunities.     

HMSPP nanocomposite and Brazilian bentonite properties after gamma radiation exposure

This work concerns the study of the mechanical and thermal behavior of the nanocomposite high melt strength polypropylene (HMSPP) (obtained at a dose of 12.5 kGy) and a bentonite clay Brazilian Paraiba (PB), which is known as “chocolate” and is used in concentrations of 5% and 10% by weight, in comparison to the American Cloisite 20A clay nanocomposites. An agent compatibilizer polypropylene-graft (PP-g-AM) was added at a 3% concentration, and the clay was dispersed using the melt intercalation technique using a twin-screw extruder. The specimens were prepared by the injection process. The mechanical behavior was evaluated by strength, flexural strength and impact tests. The thermal behavior was evaluated by the techniques of differential scanning calorimetry (DSC) and thermogravimetry (TGA). The morphology of the nanocomposites was studied with scanning electron microscopy (SEM), while the organophilic bentonite and nanocomposites were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR).     

Production of high melt strength polypropylene by gamma irradiation

High melt strength polypropylene (HMS-PP) has been recently developed and introduced in the market by the major international producers of polypropylene. Therefore, BRASKEM, the leading Brazilian PP producer, together with EMBRARAD, the leading Brazilian gamma irradiator, and the IPEN (Institute of Nuclear Energy and Research) worked to develop a national technology for the production of HMS-PP. One of the effective approaches to improve melt strength and extensibility is to add chain branches onto polypropylene backbone using gamma radiation. Branching and grafting result from the radical combinations during irradiation process. Crosslinking and main chain scission in the polymer structure are also obtained during this process. In this work, gamma irradiation technique was used to induce chemical changes in commercial polypropylene with two different monomers, Tri-allyl-isocyanurate (TAIC) and Tri-methylolpropane-trimethacrylate (TMPTMA), with concentration ranging from 1.5 to 5.0 mmol/100 g of polypropylene. These samples were irradiated with a ⁶⁰Co source at dose of 20 kGy. It used two different methods of HMS-PP processing. The crosslinking of modified polymers was studied by measuring gel content melt flow rate and rheological properties like melt strength and drawability. It was observed that the reaction method and the monomer type have influenced the properties. However, the concentration variation of monomer has no effect.     

Melt rheology of polypropylene containing small amounts of high molecular weight chain. I. Shear flow

Large enhancements of the melt strength of polypropylene (PP) were achieved by the introduction of high molecular weight polyethylene (PE) into PP. The viscoelastic properties of the high‐melt‐strength PP melts under shear flow were investigated. It was found that the rheological properties of the high‐melt‐strength PP were distinctly different from those of conventional PP. The elastic response at low frequencies was significantly enhanced in comparison with the conventional PP, implying a presence of a long relaxation time mode that was not revealed in conventional PP. In step‐shear measurements, the fast and slow relaxation processes that characterized the linear viscoelastic properties were observed also for nonlinear relaxation moduli. The dependence of the damping for the slow process of the high‐melt‐strength PP on shear strain was much weaker than that of the fast process. These rheological behaviors characterizing the long relaxation time mode were further enhanced with the increasing concentration of high molecular mass PE. The unusual shear rheological behaviors were discussed in view of the role of high molecular weight PE as a long relaxation time mode within PP. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2692–2704, 2001     

聚丙烯釜内合金性能及微观形态

通以磷酸酯化合物为内给电子体的球型齐格勒纳塔催化剂,在本体-气相聚合装置上制备了己烷可溶级分含量不同的高熔融指数的聚丙烯釜内合金,考察了其微观形态与力学性能。 结果表明,随己烷可溶组分含量的增加,冲击强度明显增加, 冲击强度从4.4 kJ/m2增加至52.7 kJ/m2,弯曲强度和拉伸强度略有减小。 拉伸强度从28.6 MPa下降至19.5 MPa,弯曲强度从37.2 MPa下降至21.5 MPa。 扫描电子显微镜照片显示,橡胶相均匀分散在聚丙烯基体中形成“核-壳”结构。     

聚丙烯接枝改性及其挤出发泡研究

以有机过氧化物为引发剂,以双螺杆挤出机为反应器,将线型不饱和聚酯(ULP)接枝到聚丙烯(PP)分子链上。通过FTIR、DSC及凝胶含量测试,对MPP的结构和性能进行了研究,表明PP发生了接枝反应;泷变性能和熔体流动速率(MFR)测定表明,接枝反应有效地改善了PP流变性能,用双螺杆挤出机对未接枝和接枝的PP进行了发泡研究,SEM分析表明接枝PP具有更好的发泡效果。     

Influence of different functionality degree grafting monomers on polypropylene melt radical branching reaction and their structure

Long‐chain–branched polypropylene (LCBPP) is one of polypropylenes (PPs) with high melt strength and good melt elasticity. Recently, due to its outstanding properties, LCBPP have been attracted increasingly attention in the field of development and characterization by the researchers all over the world. In this study, LCBPP was prepared by the melt radical branching reaction in a torque rheometer. The influences of various acrylate monomers with different functionality degrees on the structure and melt performance of PP products were investigated. The results indicated that grafting monomers with different functionality degrees made diverse influences on the branching density and branching chain length of branching PP products. With the increase of the functionality degree of grafting monomers, the branching level of PP products increased gradually and the “multiplicity” of branches became increasingly obvious. Besides, a higher reactivity of pentaerythritol triacrylate with hydroxyl than the similar molecular structured pentaerythritol tetraacrylate was confirmed. Furthermore, due to the high reactivity of dipentaerythritol penta(hexa)acrylate, branching and crosslinking reaction occurred simultaneously during the reaction process. As a result, the gel content increased and finally formed highly star branching structures with a shape of “dense and short.”     

Toughened polypropylene with balanced rigidity (II): morphology,melt flow rate and melting point of toughening master batch

The morphology of the toughening master batches (TMBs) for polypropylene (PP) was characterized by means of transmission electron microscopy and polarizing microscopy, and the melt flow rate and melting point were investigated as well. Results indicated that the TMBs prepared by using dynamic vulcanization and polymer–bridge conjunction techniques took on a very special morphology. The morphology of the TMBs was formed through microphase separation with PP component as the continuous phase, shaping very small crystallites and with elastomer component at the dispersed phase having a cellular structure containing some PP. Such a morphological characteristic is essentially different from the packaged morphology formed by flow encapsulation during the process of thermal mechanical blending. The data of melt flow rate showed that the TMBs had good processing properties adequate for being processed into polypropylene composites with both excellent toughness and balanced rigidity. The melting temperature of the TMBs determined by differential thermal analysis is lower than that PP, providing additional evidence of the chemical bonding among some elastomers and PP. Copyright © 2000 John Wiley & Sons, Ltd.