回收PE/PET共混物的原位微纤化和反应增容研究

通过原位微纤化技术和反应增容,制备了含回收聚对苯二甲酸乙二醇酯(PET)、低密度聚乙烯(LDPE)和线性低密度聚乙烯(LLDPE)以及高密度聚乙烯(HDPE)的原位微纤化共混物(MRB).探讨了原位成纤作用下,相容剂马来酸酐接枝聚乙烯(PE-g-MAH)用量对共混物力学性能的影响,同时利用差示扫描量热仪(DSC)和扫描电镜(SEM)研究了含4份PE-g-MAH共混物的非等温结晶特性和共混物形态.结果表明,成纤和增容双重作用对共混物的拉伸强度、断裂伸长率、弯曲模量和弯曲强度都有提高,而冲击强度有所下降;微纤对基体聚乙烯结晶有促进作用且注塑共混物比拉伸共混物更明显.HDPE与LLDPE发生了共结晶;拉伸共混物中的微纤比注塑共混物中的微纤长.     

原位微纤化方法回收PET与PE-HD混合物的形态研究

通过多次挤出,模拟了材料的多次回收过程,研究了用原位微纤化方法回收聚对苯二甲酸乙二醇醋/高密度聚乙烯(PET/PE-HD)共混物的形态变化,并探讨了引起形态变化的因素。实验发现,通过“熔融挤出一热拉伸一淬冷”,PET、分散相形成了明显的微纤结构,经过多次挤出后,PET微纤的平均直径增加,第1次挤出后仅为0. 89 urn,第4次挤出后增加到2. 84 μm,增加了约219.1%。这是回收的PET, PE-Hl)发生了降解,使两者的豁度比增加,同时氧化使两相作用增强所致。     

相容剂对PE-HD／PET共混合金性能的影响

以乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯三元共聚物（PTW）作为高密度聚乙烯（PE-HD）／聚对苯二甲酸乙二醇酯（PET）共混合金的反应性相容剂，采用熔融挤出法制备了以PE-HD为基体的PE～Hi）／PET、共混合金。通过力学性能和流变性能测试，扫描电镜（SEM）和动态力学分析（DMA）等手段，研究丁PTW对共混合金性能的影响。结果表明：PTW提高了体系的综合性能，当PE-HD／PET配比为90／10，PTW含量在5份时，其缺口冲击强度提高了近400％，拉伸强度和断裂伸长率分别提高了25％和50％，同时改善了共混合金的加工性能。SEM分析表明PTW的加入增大了共混合金的界面相互作用，促进了分散相粒子的细化，从而提高丁体系相容性，DMA测试表明，PTW的加入使PET的玻璃化转变温度向PE—HD的玻璃化转变温度靠近：     

具有原位导电微纤网络的CB／PET／PE复合材料的力学性能

在前期热塑性塑料原位成纤研究的基础上，尝试利用原位成纤方法制备炭黑(CB)／聚对苯二甲酸乙二醇酯(PET)／高密度聚乙烯(HDPE)原位导电微纤网络复合材料(CEMN)，以期增强复合体系的力学强度。通过对CEMN体系与CB／PE体系的力学性能测试发现，CEMN体系的拉伸强度低于普通CB／PE复合物。为增强复合体系的力学性能，应改变加工过程及降低体系中CB的用量。     

PP／PET／EPDM-g-GMA共混物结构与性能研究

通过反应共混制备了PP／PET／EPDM—g-GMA共混物。用扫描电镜和图像处理软件对共混物形貌进行定性和定量分析，用偏光显微镜观察共混物等温结晶形态，最后测量共混物的力学性能。结果表明：在PP／PET共混物中加入EPDM-g—GMA后，两相相容性改善，进一步加入成核剂后分散相尺寸更小、粒径分布更均匀；PP球晶随PET的混入而减小；在PP／PET体系中加入EPDM-g—GMA起到反应增容和橡胶增韧的协同效应，使缺口冲击强度由未加增容剂时的2．0kJ／m^2提高至6．6k．1／m^2，弹性模量较PP提高了38％；PP／PET共混物的拉伸强度随PET含量的增加下降，在相同PET含量的情况下，加入EPDM—g-GMA后，共混物的拉伸强度与未增容体系基本一致。     

PBT含量对PLA/PBT原位微纤复合材料流变及发泡性能的影响

聚乳酸(PLA)是用量最大的可生物降解材料之一,由于其拉伸流变性能较差,难于发泡。本文采用聚合物微纳层叠共挤装置制备PLA/聚对苯二甲酸丁二醇酯(PBT)原位微纤复合材料(PLA/PBT-MRC),研究了PLA/PBT-MRC的微纤形态、熔体的动态流变性能和拉伸流变性能。PLA、PLA/PBT-MRC注塑发泡后的泡孔形貌、注塑发泡制品的拉伸、缺口冲击和弯曲力学性能。研究表明：PLA/PBT-MRC中微纤宽度低至0.72μm,宽度随PBT含量增加而增大;随PBT含量增加PLA/PBT-MRC的储能模量、损耗模量和复数黏度都增大;PBT含量增加可以明显改善PLA熔体的拉伸流变性能,相对PLA表现出明显的拉伸应变硬化;PLA/PBT-MRC注塑发泡后泡孔直径比PLA注塑发泡泡孔直径减小800%,泡孔密度增加600%,发泡制品的拉伸强度、缺口冲击强度、弯曲强度分别提高22.2%、10.1%和26.4%。     

HDPE/r-PET原位微纤物微观形态与力学性能

以高密度聚乙烯(HDPE)和回收聚对苯二甲酸乙二醇酯(r-PET)为原料,通过反应挤出、冷拉伸、退火工艺制备了HDPE/r-PET原位微纤物。研究了扫描电镜(SEM)的制样方法即用液氮冷冻、脆断样品、聚四氟乙烯带包覆、在沸腾的二甲苯中刻蚀7～10min和不同r-PET用量、不同拉伸比制备出的系列HDPE/r-PET原位微纤物的力学性能。结果表明,通过SEM可清晰地看到形成的微纤,原位微纤物的拉伸强度和冲击强度都随拉伸比的增大而增大;r-PET质量分数为15%时,原位微纤物的拉伸强度和无缺口冲击强度达到最大值;HDPE/r-PET原位微纤物的适宜注塑温度为210℃。     

表面处理纳米铜粉/PET共混物的流变性能

采用硅烷偶联剂KH-550对纳米铜粉进行表面处理,通过熔融共混制备纳米铜粉/PET共混物,用毛细管流变仪研究了共混物的流变性能。结果表明:纳米铜粉/PET共混体系为非牛顿性假塑性流体,其表观黏度随着剪切速率的增大而减小;随着纳米铜粉含量增加,非牛顿指数增大;共混物的黏流活化能随剪切速率的增加而减小。     

Surlyn对PET及其共混体系流变与结晶性能的影响

通过熔融共混法制备了聚对苯二甲酸乙二醇酯 (PET)/聚酰胺6 (PA6)/Surlyn与PET/均苯四甲酸酐 (PMDA)/Surlyn共混材料,研究了Surlyn对共混体系的形貌以及共混体系中PET流变性能与结晶性能的影响。并使用扫描电子显微镜 观察了PET/PA6/Surlyn共混物的低温淬断断面,使用旋转流变仪与差示扫描量热仪研究共混物的流变性能与结晶性能。结果表明,Surlyn可以提高PET/PA6/Surlyn共混体系的熔体强度,促进共混体系中PET的结晶,使PET结晶温度提高10 ℃,过冷度与结晶半高宽显著下降,明显改善PET的流变性能与结晶性能,而对于PMDA扩链后的PET,Surlyn对其结晶性能的影响影响较小;Surlyn可以降低PA6分散相的粒径,提高PET与PA6两相之间的相容性。     

增容剂对PP/PET原位微纤化共混物的影响

通过"熔融挤出-热拉伸-淬冷"的方法制备了原位微纤化共混物。采用扫描电镜、差示扫描量热仪和力学性能测试等方法研究了增容剂PP-g-GMA含量对共混物微观形态、力学性能和结晶性能的影响。结果表明,增容剂的加入可明显提高两相相容性,改善界面效果,明显降低拉伸前初始粒子的尺寸,但同时使拉伸后形成的微纤呈现一定的损坏,长径比有所降低。增容剂可以明显改善微纤化共混物力学性能,当其含量为2 %（质量分数,下同）时拉伸强度比未增容试样提高了11.0 %,弯曲强度都提高了11.3 %;当其含量为6 %时冲击强度也比未增容共混物提高了34.5 %。此外,PET微纤对PP有很好的异相成核作用,使其结晶温度提高了16.3 ℃,结晶时间为纯PP的32 %左右,而增容剂的加入使共混物中PP的结晶时间延长。     

Morphology and Rheological Behaviors of Polycarbonate/High Density Polyethylene in situ Microfibrillar Blends

Summary: Polycarbonate (PC)/high density polyethylene (HDPE) in situ microfibrillar blends were fabricated by a slit die extrusion, hot stretching, and quenching process. Despite PC and HDPE having a high viscosity ratio, which is usually disadvantageous to fibrillation, the morphological observation indicated that the blends had well‐defined PC microfibrils. The size and amount of the PC fibrils were nonuniform through the thickness of the extrudate, and were also affected by the PC concentration and hot stretch ratio. There were coarse and dense fibrils in the core zone, while these fibrils became finer and reduced in number toward the surface. The melt flow rate (MFR) of the PC/HDPE microfibrillar blend decreased with the increase of PC concentration, but increased with the larger hot stretching rate (or hot stretching ratio, HSR). Besides, it was found that the fibrillar blend had better flowability than the common blend with spherical particles at the same PC concentration. Temperature was also an important factor influencing the MFR due to the temperature dependence of PC and HDPE viscosity, and the PC phase morphology. The PC microfibrils could not be preserved beyond 230 °C and transformed into spherical particles. The rheological behaviors at various shear rates were studied by capillary rheometer. The orientation of PC fibrils and HDPE molecules with higher shear rate led to a decrease in the viscosity of microfibrillar blend. The data obtained in this study can help construct the technical foundation for recycling and utilization of PC and HDPE waste by manufacture of microfibrillar blends in future work.

SEM micrograph of the PC/HDPE microfibrillar blend.     

Recyclability of In Situ Microfibrillar Poly(ethylene terephthalate)/High‐Density Polyethylene Blends

Repetitive processing was employed to assess the recyclability of in situ microfibrillar poly(ethylene terephthalate) (PET)/high‐density polyethylene (HDPE) blends which were fabricated through a “rectangular slit die extrusion–hot stretching–quenching” process. For comparison, the conventional PET/HDPE blends were also obtained using the same processing operation but without hot stretching. The morphological observation indicated that slit die extrusion and hot stretching successfully made the dispersed PET phase deform in situ into well‐defined microfibrils. The average diameter of the microfibrils increased with the processing cycles. The rheological properties obtained from the parallel‐plate dynamic rheometer suggested that the microfibrillar blends have higher viscosity and viscoelastic moduli (storage and loss moduli) as well as better flow stability than the conventional PET/HDPE blend. More importantly, with the increase in the processing cycles, an increase in yield strength and unchanged tensile modulus were observed for in situ microfibrillar blends, while a decrease in these properties for conventional blend, indicating that the in situ microfibrillar PET/HDPE blends have promising recycling potential.

     

Melt rheological properties of reactive compatibilized HDPE/PET blends

Melt rheological properties of high density polyethylene and poly(ethylene terephthalate) (HDPE/PET) blends compatibilized by an ethylene–butyl acrylate–glycidyl methacrylate terpolymer (EBAGMA) were studied by means of a HAAKE torque rheometer and a capillary rheometer. The phase morphology of the blends was evaluated by a scanning electron microscope (SEM). The results showed that the melts of blends behave pseudoplasticity. The addition of EBAGMA strengthens the interfacial adhesion between HDPE and PET and improves the phase dispersion due to reactive compatibilization. It was observed that the balance torque, melt viscosity, and sensitivity of melt viscosity to shear rate of the melts increase with increasing content of EBAGMA, but the melt flow index and activation energy decrease. At the same time, the plasticizing time is shortened indicating that the processability of the compatibilized blends has been improved. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

In situ compatibilization of HDPE/PET blends

The reactive compatibilization of immiscible polymers such as high‐density polyethylene (HDPE) and poly(ethylene terephthalate) (PET) by interfacial grafting of maleic anhydride (MA) without initiator in the molten state was investigated in this study. Grafting reaction of MA onto HDPE was carried out in a Rheocord HAAKE mixer varying reaction parameters such as the temperature, the shear rate, and the time of reaction. Then, the purified copolymers were characterized by infrared spectrometry and the MA content of HDPE‐g‐MA copolymers was determined by volumetric titration. It has been shown that thermomechanical initiation is sufficient to reach grafting yield of 0.3 to 2.5 wt % of MA. We studied then the compatibilization of HDPE/PET blends by interfacial grafting of MA. The in situ interfacial reaction leads to the formation of HDPE‐g‐MA copolymer which acts as a compatibilizer in the blends. The foremost interest of this work is that it provides a simple way of compatibilization of immiscible blends of polyolefin and polyester in one transformation step without using free‐radical initiators. The mechanical properties of the blends are strongly improved by the addition of small quantities of MA. The SEM observations of the compatibilized blends show a deep modification of the structure (i.e., enhanced regularity in the nodule dispersion and better interfacial adhesion). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 874–880, 2001     

PE-HD/纳米SiO_2复合材料的动态流变行为研究

研究了高密度聚乙烯(PE-HD)/纳米二氧化硅(SiO_2)复合材料的动态流变行为,探讨了纳米 SiO_2经表面偶联剂处理对复合体系的流变行为影响。实验数据显示,PE-HD/SiO_2体系是假塑性流体,黏度随着 SiO_2含量的增加而增加,当>6%时,黏度发生突变,并出现强烈的剪切变稀,在动态储能模量(G′)、损耗模量(G″)与频率(ω)关系曲线上分别出现第二平台,表明体系因粒子间相互关联、团聚及粒子与基体问相互作用而形成局部有序的逾渗网络结构。而纳米 SiO_2经偶联剂处理后,体系流体类型没有改变,体系黏度下降,对应的 G′、G″与ω关系曲线上没有出现第二平台,复合体系更加均匀。     

PET／沸石分子筛复合材料制备及结晶行为与热性能研究

通过熔融共混方法制备了聚对苯二甲酸乙二醇酯(PET)/沸石分子筛复合材料,考察了沸石分子筛在PET中的分散状态;从定性和定量两个方面研究了其结晶行为和结晶动力学;分析了其热稳定性。结果表明,沸石分子筛在PET中分散良好;沸石分子筛对PET具有很好的成核效果和加速PET结晶的作用,平均结晶速率是纯PET的2～3倍;热稳定性也比纯PET有较大幅度提高。