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。     

高熔体强度聚丙烯及发泡珠粒的制备与研究

使用直接聚合法制备了具有宽分子量分布的高熔体强度聚丙烯。利用反应釜浸渍法,以上述高熔体强度聚丙烯为基础树脂可以制备聚丙烯发泡珠粒。利用扫描电子显微镜和熔体强度测试仪考察了聚丙烯发泡珠粒的制备工艺及基础树脂的熔体强度对泡孔结构的影响。结果表明,与普通商业化聚丙烯如T30S相比,较高的熔体强度有利于泡孔结构的控制。     

α-烯烃基甲基二氯硅烷调控丙烯多相共聚制备高熔体强度高抗冲聚丙烯

作为最重要的热塑性高分子材料之一,聚丙烯在材料力学性能上的缺陷主要表现为冲击韧性尤其是低温韧性差,在熔体加工中的缺陷主要表现为熔体强度低,如何综合改善这两方面的性能是丙烯聚合和聚丙烯结构设计研究的重要问题.本文利用α-烯烃基甲基二氯硅烷调控丙烯多相共聚,在聚合反应完成后通过对聚合物进行水解处理,在共聚物中产生长链支化结构,制备了同时具有高熔体强度和高冲击韧性的新型聚丙烯.共聚物的凝胶渗透色谱(GPC)和熔体流变学测试结果均表明长链支化结构的存在,而试样断面扫描电镜(SEM)则清楚给出其以聚丙烯为基体和以乙丙无规共聚物橡胶(EPR)为分散相的相分离形态.共聚物在拉伸流变测试中表现出高熔体强度和显著的应变强化效应,在力学性能测试中显现出高缺口冲击强度.     

界面改性剂在聚丙烯／高岭土二相复合体系中的作用

从高岭土（Ｋａｏｌｉｎ）填充聚丙烯（ＰＰ）体系的界面分子设计入手，研究了界面改性剂对填料的分散性，聚丙烯基体的结晶行为，填充熔体流变性质以及材料力学性能的影响．结果表明，界面改性剂降低了填料的高表面能，改善了填料分散状况．界面改性剂的加入，填充熔体粘度接近纯聚丙烯数值．经界面改性剂处理后，填充材料缺口悬臂梁冲击强度随填料量的增加而急剧升高，在填料量为３０Ｗｔ％时，冲击强度达到４８０Ｊ／Ｍ，是未处理材料的十二倍，添加至填料量为５０ｗｔ％时，冲击强度没有明显降低．     

聚丙烯及增韧剂对复合材料熔接痕强度的影响

研究了聚丙烯基体的熔体粘度(以熔体流动速率表征)、增韧剂POE的粘度(以门尼粘度表征)、增韧剂POE的含量等因素对聚丙烯复合材料熔接痕强度的影响。结果表明:聚丙烯基体/增韧剂的粘度比越小,聚丙烯复合材料的熔接痕强度越高,即聚丙烯粘度越小、增韧剂粘度越大,整个复合材料的熔接痕强度越高;增韧剂POE的含量越大复合材料的熔接痕强度越小。     

聚酰胺6／聚醚砜共混体系的结晶与熔融行为

聚醚砜（ＰＥＳ）是一种非晶特种工程塑料，具有强度好，使用温度高等特点，但熔体粘度高，加工上有一定困难．聚酰胺６（ＰＡ６）是部分结晶的工程塑料，有很好的强度和耐磨性能．加入适量的ＰＡ６，可显著地降低ＰＥＳ的熔体粘度，且可基本保持ＰＥＳ的原有性能［１］．...     

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.     

硬脂酸/异氰酸酯摩尔比对聚丙烯/木粉复合材料性能的影响

用甲苯-2,4-二异氰酸酯（TDI）和硬脂酸（SA）复合改性木粉,在双螺杆挤出机中制备了聚丙烯（PP）基的木塑复合材料（WPC）,研究了SA/TDI摩尔比对木粉表面性能、复合材料力学性能和加工性能的影响。 结果表明,随着SA/TDI摩尔比的增大,改性木粉的表面张力逐渐减小,与PP的界面张力先减小后增大;与未改性的WPC相比,SA/TDI复合改性剂对WPC的拉伸强度、弯曲强度、缺口冲击强度影响不明显,但对无缺口冲击强度提升较大;当SA/TDI摩尔比为1.07时,复合材料的无缺口冲击强度和熔体质量流动速率分别达到9.74 kJ/m2和13.12 g/10 min,分别比未改性WPC提高了77%和22%。     

熔体自由基反应法制备聚丙烯/碳纳米管复合材料

以2,5-二甲基-2,5-双（叔丁基过氧基）己烷（DHBP）在聚丙烯体系中引发形成自由基,以二硫化四甲基秋兰姆（TMTD）调控自由基反应,通过熔融共混一步法制备了共价接枝的聚丙烯/碳纳米管（PP/CNTs）复合材料。 通过拉曼光谱和透射电子显微镜证明发生了共价接枝反应,并研究了PP/CNTs的结晶性能、热性能与力学性能。 结果表明,发生共价接枝的PP/CNTs与未接枝的PP/CNTs及PP相比,其结晶温度分别提高了2.6和12.0 ℃,热分解温度T5%分别提高了6.4和34.8 ℃,其拉伸强度和拉伸模量略有提高,冲击强度分别提高了56.7%和58.1%。     

Ziegler-Natta催化剂的功能化及聚烯烃高性能化

介绍了Ziegler-Natta催化剂功能化的几种策略,以及其应用于聚烯烃高性能化的研究进展。Ziegler-Natta催化剂/先进聚合助剂复合策略可有效扩展Ziegler-Natta催化剂性能,其中Ziegler-Natta/ω-烯烃甲基二氯硅烷功能催化剂体系在制备长链支化/高熔体强度聚丙烯方面已显示出工业潜力,而Ziegler-Natta/非共轭α,ω-双烯烃体系为丙烯多相共聚提供了革命性的技术,使丙烯多相共聚不但可生产高抗冲聚丙烯(低橡胶含量),也可生产聚丙烯基热塑性弹性体(高橡胶含量)。Ziegler-Natta/茂(非茂)复合催化剂和纳米负载Ziegler-Natta催化剂可进一步丰富Ziegler-Natta催化剂性能,制备新型高性能聚烯烃材料。     

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).     

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。     

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.     

Basis of Solid-Phase Grafting of Polypropylene

Abstract

The chemical modification of polymers opens new dimensions for the development and design of materials based on plastics. The chemical modification of polymers by reactions is performed by reactions in a melt, in a solution, or in a solid phase. The modification of polymers in solid phases (powder or granular material directly from the polymerization) has great advantages compared with reactions in solution or melt. The advantages are lower costs and, most important, greater creative variability. A special advantage of solid-phase modification of polypropylene (PP) is the fact that the degradation reaction is reduced.     

Melt‐extensional properties and orientation behaviors of polypropylene‐layered silicate nanocomposites

Polypropylene‐layered silicate nanocomposites consisting of three components—pure polypropylene, maleated polypropylene, and organically modified silicate—were prepared by the melt‐intercalation method to investigate melt‐extensional properties such as melt strength, neck‐in test, and orientation behavior. The nanocomposites showed an enhanced tensile modulus, enhanced storage modulus, much enhanced melt tension, and reduced neck‐in during the melt processing as compared with neat polymer. The uniaxial drawing induced the silicate surface to align parallel to the sheet surface. The c and a* axes of the polypropylene crystals were bimodally oriented to the flow direction, and the b axes were oriented to the thickness direction. The bimodal orientation of the polypropylene crystal was enhanced with the concentration of silicates. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 158–167, 2005     

多官能团单体对马来酸酐接枝聚丙烯流变行为的影响

研究了多官能团辅助单体偏苯三酸三丙烯酯(TATM)对马来酸酐接枝聚丙烯的熔体流动速率(MFR)和流变行为的影响.当以不含抗氧剂的聚丙烯粉料为原料时,TATM的加入对稳定接枝产物MFR的效果并不理想.但将聚丙烯粉料添加抗氧剂并造粒后,TATM的加入则可有效稳定体系的MFR,各种流变曲线显示出接枝产物的熔体弹性明显提高,说明有枝化或交联结构出现.针对PP粉料和粒料间接枝产物流变行为存在的重大差异,结合熔体自由基接枝反应的机理进行了解释.TATM能够起到稳定MFR的效果是由于其提高了接枝物的熔体弹性,从而抵消了聚丙烯熔体接枝反应中所不可避免的β断链所造成的剪切黏度下降.聚丙烯粉料和粒料中抗氧剂的差异对聚丙烯的加工降解有严重影响,造成了TATM在不同聚丙烯体系中效果的差异.     

PP熔融接枝改性研究进展

聚丙烯作为一种非极性聚合物,其亲水性、染色性、粘结性及与其它极性聚合物和无机填料的相容性都很差,这大大限制了它的应用。因此,往往采用官能化的方法赋予聚丙烯以极性、反应活性和功能性。通过熔融接枝的方法,在聚丙烯链段上接枝极性单体,可以显著提高聚丙烯的极性,改善表面亲水性及染色性等。本文简要介绍了聚丙烯熔融接枝改性及其影响因素,并按接枝单体分类,综述了熔融接枝聚丙烯的研究进展、性能与应用,展望了其发展趋势。     

聚丙烯与聚酯-聚醚多嵌段共聚物共混的研究

聚丙烯和聚酯-聚醚多嵌段共聚物的熔融共混物是微多相分散体系,其力学性能和软链段的结构有关。DSC和偏光显微镜图分别表明共混物中聚丙烯结晶度以及球晶尺寸随聚酯-聚醚的混入量而变小。聚丙烯和少量聚酯-聚醚多嵌段共聚物共混,可改进聚丙烯的流变性,吸湿性和染色性。