The preparation and rheology characterization of long chain branching polypropylene

In order to study the rheological behavior of long chain branching (LCB) polypropylene (PP), linear polypropylene was modified by melt grafting reaction in the presence of 2,5-dimethyl-2,5(tert-butylperoxy) hexane peroxide and pentaerythritol triacrylate (PETA) in mixer. The transient torque curves and Fourier transformed infrared spectroscopy (FTIR) results indicated that macroradical recombination reactions took place and PETA had been grafted onto PP backbone. Various rheological plots including viscosity curve, storage modulus, loss angle, Han plot, Cole-Cole plot were used to distinguish LCB PP from linear PP. On the other hand, to quantify the LCB level in modified PPs, a new method was suggested on the basis of macromolecular dynamics models. The results showed that the level of LCB was in the range of 0.025-0.38/10⁴ C . Moreover, the length of the branched chains and the content of the branched component increase with PETA concentration. Furthermore, the LCB efficiency of monomer can also be calculated, less than 20% of grafting monomers was used to form branch structure.     

长链支化制备高熔体强度PP的研究

通过长链支化来改性PP，从而得到高熔体强度的PP。实验以丙烯酸酯类单体为接枝单体，过氧化物为引发剂，对PP进行了熔融接枝，重点考察了二官能团单体的改性情况。实验结果表明，二三官能团单体的改性效果较为明显；熔体流动速率随单体加入量增加而降低，随过氧化物浓度增加而升高；拉伸粘度谱图显示有明显的应变硬化现象；改性后产物的熔体强度变化明显；纯化后的产物经工外，差示扫描量热分析表明接枝反应的发生；索氏萃取法没有检测到凝胶的生成。     

长链支化聚丙烯的反应挤出制备及其流变和热力学性能研究

在过氧化引发剂和季戊四醇三丙烯酸酯(PETA)存在下,采用反应挤出法制备了长链支化聚丙烯（LCB-PP）。用旋转流变仪和差示扫描热法系统研究了纯的和改性PP的流变性能和热力学性能,并考察了不同过氧化引发剂对改性PP的性能和支化情况的影响。研究发现,单纯使用过氧化引发剂改性时,PP以降解为主;加入多功能单体PETA后,PP以接枝反应为主。流变行为研究发现,过氧化引发剂/PETA改性的PP,其流变性能呈现如低频处储能模量增大,剪切变稀行为明显,损耗角随频率变化出现平台区,零剪切黏度增大等特点,证明改性PP存在长链支化结构,通过公式计算发现改性PP的支化度较高。差士扫描量热分析表明,过氧化引发剂/PETA改性PP的结晶温度高于纯PP,这也说明改性PP存在长链支化结构。同时发现过氧化引发剂/PETA改性PP时,过氧化引发剂结构对改性PP的流变性能、热力学性能和支化度影响较小。     

Efficiency of plasticization of PVC by higher-order di-alkyl phthalates and survey of mathematical models for prediction of polymer/diluent blend Tg's

Presently, a suitable theory to predict the T_g vs. composition relationship for a given polymer-plasticizer blend, based on detailed molecular structure and molecular energitics considerations, is not available. In particular, the plasticizer efficiency parameter, k, which is uniquely defined at low-to-moderate diluent concentrations, and is an essential variable in the Mauritz-Storey theory of the diffusion of large molecules in amorphous polymers in the rubbery state, must always be determined by experiment. In this work, k was determined by DSC for PVC that was plasticized over a range of concentrations with a number of higher branched and linear di-alkyl phthalates. The results will be used in our plasticizer diffusion theory as well as provide guidance in the future development of a general mathematical model for predicting k. It was seen that k decreased with increasing molecular weight for both the linear and branched phthalates. For a given molecular weight, the branched phthalates have higher k values than the linear structures. These results have been rationalized in terms of the additional free volume created by the inefficiency of packing polymer chains about these large penetrant molecules. The DSC scans also implied an increasing degree of microstructural heterogeneity with increasing plasticizer concentration. Finally, relationships between plasticizer diffusion coefficient in the rubbery state and the plasticized T_g were established for low-to-moderate diluent concentration for three of the plasticizers studied by utilizing experimental diffusion data from our earlier work on these systems.     

Curing kinetics and thermal properties of vinyl ester resins

The curing kinetics of dimethacrylate-based vinyl ester resins were studied by scanning and isothermal DSC, gel time studies, and by DMTA. The rate of polymerization was raised by increased methyl ethyl ketone peroxide (MEKP) concentration but the cocatalyst, cobalt octoate, retarded the reaction rate, except at very low concentrations. By contrast, the gel time was reduced for all increases in either peroxide or cobalt concentration. This contradictory behavior was explained by a kinetic scheme in which the cobalt species play a dual role of catalyzing the formation of radicals from MEKP and of destroying the primary and polymeric radicals. The scanning DSC curves exhibited multiple peaks as observed by other workers, but in the present work, these peaks were attributed to the individual influence of temperature on each of fundamental reaction steps in the free radical polymerization. Physical aging appeared to occur during the isothermal polymerization of samples cured below the “fully cured” glass transition temperature (T_g). For these undercured materials, the difference between the DSC T_g and the isothermal curing temperature was approximately 11°C. Dynamic mechanical analysis of a partially cured sample exhibited anomalous behavior caused by the reinitiation of cure of the sample during the DMTA experiment. For partially cured resins, the DSC T_g increased monotonically with the degree of cure, and this dependence was fitted to an equation related to the Couchman and DiBenedetto equations. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 769–781, 1997     

Reactive extrusion of polyolefin ternary blends

Reactive extrusion of polypropylene (PP)/ethylene–propylene–diene terpolymer (EPDM)/high-density polyethylene (PE) (80/10/10 by weight) blends were carried out using a corotating twin-screw extruder. The effects of peroxide and coagent concentrations and extruder rpm were studied in terms of rheological, morphological, thermal, and mechanical properties of the blends. Melt viscosity of the peroxide-treated blend increased and decreased over the untreated one depending on the amount of a coagent. Morphologically, interfaces blur with only a peroxide treatment, and significant domain reduction was obtained when peroxide and a coagent were used together. Both T_m (crystalline melting temperature) and T_g (glass transition temperature) of PP increased in the blend, whereas those of PE slightly decreased. © 1996 John Wiley & Sons, Inc.     

Effect of additives on the composition dependent glass transition variation in PS/PP blends

The effect of additives on glass transition behavior in melt processed blends of polystyrene (PS) and polypropylene (PP) was studied. Blends of additive‐free polystyrene and additive‐free polypropylene revealed the known effect of the PS T_g increase in blend compositions where PP surrounds PS. Glass transition behavior in these blends was compared to blends prepared from additive‐free PP and commercial grade PS, which contained lubricant additives. The thermal transitions of PS and PP were measured using modulated DSC. Although the behavior of low PS concentration blends was similar in both systems, the characteristics of the high PS blends differed substantially. These differences and the contrast in the PP T_g behaviors were attributed to the migration of additives from the PS phase across the immiscible interface into the PP phase. Similar T_g variations were observed in blends of commercial grade PS and commercial grade PP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

长链支化聚丙烯的制备及其熔体流变性能的研究

在过氧化物引发剂和季戊四醇三丙烯酸酯存在下,利用反应挤出法制备了长链支化聚丙烯(LCB-PP)。采用熔体流动速率(MFR)仪、旋转流变仪和熔体强度测试仪对纯聚丙烯(PP)及其改性PP进行测试与表征。讨论了不同的过氧化物引发剂对改性PP流变性能的影响。结果表明,采用过氧化苯甲酰时,改性PP具有较高的熔体强度、较低的MFR,并且在低频处储能模量增大。同时发现,随温度的升高,改性PP的熔体强度逐渐降低,但升高到一定温度后,熔体强度的变化不明显。     

Electrically conducting polypropylene/polyaniline‐grafted‐short glass fiber composites: Microstructure and dynamic mechanical analysis

The thermal properties of isotactic polypropylene (iPP) reinforced with polyaniline‐grafted‐short glass fibers (PAn‐g‐SGF) at 10, 20, and 30 wt% concentration and iPP blended with 5 wt% PP‐grafted‐maleic anhydride (PP‐gMA) and 30 wt% of PAn‐g‐SGF were investigated. iPP crystallizes into a spherulitic morphology, the microfiller promoted larger spherulite size and higher dynamic modulus, but the overall degree of crystallinity decreased as the concentration of PAn‐g‐SGF increased. The melting temperature, T_m, was not influenced by the microfiller. However, the crystallization temperature, T_c, as determined by DMA, first decreased reaching a minimum at ca. 20 wt%, and then increased, in contrast with T_c determined by DSC, it increased as concentration increased. The initial reduction in T_c observed by DMA seems to be associated with the crystallites growing from the microfiller into the matrix, the overall molecular dynamics then being less affected. On the other hand, increase in T_c above 20 wt% concentration suggests that the percolation threshold could be responsible for these results. Addition of the maleic anhydride copolymer produced higher shear modulus, transition temperatures, and activation energy, suggesting higher interaction between microfiller and polymer matrix. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Interaction of self‐nucleation and the addition of a nucleating agent on the crystallization behavior of isotactic polypropylene

The relationship between heterogeneous or homogeneous nucleation and self‐nucleation of polypropylene (PP) and PP nucleated by an organic phosphate salt (PPA) was studied by DSC. For pure PP, it homogeneously nucleated during cooling after melting at the selected temperature (T_s) of 170–200°C for 3 min, but at the T_s of 160–168°C self‐nucleation occurred; PPA only nucleated heterogeneously at the T_s of 168–200°C, and there existed self nucleation at the T_s of 160–168°C. The double melting peaks of PP and PPA at the T_s of 162°C were observed. Once the self‐nucleation occurred, the change of the crystallization temperature and heat of fusion of PP is more significant than that of PPA with the change of the T_s, depending upon the crystallization conditions. Results were explained by homogeneous nucleation, heterogeneous nucleation, self‐nucleation, and annealing crystallization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 78–84, 2001     

Crosslinking of polypropylene–polyethylene blends by peroxide and the effect of pentaerythritol tetrallyl ether

Crosslinking of polypropylene–polyethylene (PP-PE) blends involving 10, 20, 30, 40, 50, 60, 70, 80, and 90% of PP with dicumylperoxide (DCP) or tert-butyl perbenzoate (TBPB) and in the presence of coagent pentaerythritol tetrallyl ether (PETA) was investigated at 180°C. It was found that at lower concentrations of peroxide alone (e.g., 2.5% of DCP) only PE component is crosslinked in all compositions of PP-PE blends. In the crosslinking of PP-PE 50:50 with 4% of TBPB, insoluble gel was obtained, which contained 13% PP and 87% PE. If 2% PETA was also used, the portion of PP in gel increased to 39%; the total yield of gel in PP-PE blend increased from 50 to 70%. The lower crosslinking efficiency of coagent PETA in the PP-PE blends compared with PP alone is associated with better solubility of the coagent in the PE phase in contrast to the PP phase. The coagent does not particularly raise the crosslinking efficiency of peroxide in PE, but increases it in the PP phase. A remarkable decrease in melting temperature and temperature of crystallization of both polymer components depending on peroxide concentration was found by calorimetric measurements.     

A study of radical graft copolymerization on polypropylene during extrusion using two peroxide initiators

Functionalization of polypropylene (PP) during melt extrusion has been explored extensively. In this study, two different radical initiators were employed and compared in grafting acyclic halamine precursors to PP. 2,4‐Diamino‐6‐diallylamino‐1,3,5‐triazine (NDAM) was grafted onto PP during a melt‐extrusion process using either 2,5‐dimethyl‐2,5‐(tert‐butylperoxy)hexyne (DTBHY) or dicumyl peroxide (DCP) as initiator. The results confirmed the radical graft copolymerization of the monomer onto the PP backbone during the reactive extrusion process. It was revealed that, at low monomer concentration, when peroxide initiator concentration was increased, polymer chain scission became dominant. DCP was more efficient than DTBHY as an initiator in the graft polymerization. After exposure to chlorine bleach, the grafted structures could be easily transformed into N‐halamines, which provided powerful, durable and regenerable antibacterial activities against Escherichia coli and Staphylococcus aureus. It is concluded that both DCP and DTBHY could be used as radical initiators in reactive extrusion to graft certain vinyl monomers to PP. The NDAM‐grafted PP could provide expected antibacterial function after chlorination of the grafted product in a chlorine bleach solution. The modified PP showed great potential for use in medical devices and non‐woven textiles. Copyright © 2009 Society of Chemical Industry     

Effect of viscosity ratio,rubber composition,and peroxide/coagent treatment in PP/EPR blends

Effect of Viscosity ratio (ηEPR/ηPP), propylene (C₃) content of (ethylene-propylene copolymer (EPR)), and peroxide/coagent treatment on polypropylene (PP)/EPR (80/20 by weight) melt blends were studied in terms of morphological, rheological, thermal, and mechanical properties. As the viscosity ratio increases from approximately 0.8 to 1.2, domain size increased (submicron-1.5 μm), and the degree of supercooling (ΔT) for crystallization increased (37.4–47.8°C) due to the decreased crystallization temperature (T_cc, 122.2–110.8°C). This resulted in larger spherulite size and increased hardness, modulus, and yield strength. With high C₃ EPR, total crystallinity (ΔH_f) of PP decreased, together with the mechanical properties, except the impact strength. With peroxide/coagent treatment, the spherulite size significantly decreased. The notched Izod impact strength decreased with increasing viscosity ratio, but significantly increased with high C₃ EPR and with peroxide/coagent treatments. The results were interpreted in terms of domain size and shape, chemical affinity between PP and EPR, copolymer formation, and main chain scission of PP. © 1996 John Wiley & Sons, Inc.     

PETA/St双单体聚丙烯挤出改性及其发泡性能研究

以季戊四醇三丙烯酸酯（PETA）和苯乙烯（St）为接枝单体,采用反应挤出改性制备具有长支链结构的聚丙烯（LCBPP）。使用红外光谱、差示扫描量热仪、流变测试等表征材料的可发泡性,并通过扫描电子显微镜观测发泡材料的泡孔形貌。并以CO₂为发泡剂进行了间歇熔融发泡实验以评估聚丙烯（PP）的熔融发泡性。结果表明,在未交联改性PP中,用2 %（质量分数,下同）PETA和3 %St改性的PP各项性能最好;改性PP具有不同程度的应变硬化现象,这归因于不同程度的长链支化结构;改性后具有长链支化结构的PP有较好的发泡效果,PP?g?PETA/St样品的发泡温度窗口为25 ℃,最高发泡倍率达到33倍,此时泡孔平均直径为36 μm,泡孔密度为3.17×10⁸个/cm³。     

Microstructure and properties of polypropylene/glass fiber composites grafted with poly(pentaerythritol triacrylate)

Isotactic polypropylene(PP)/glass fiber(GF) composites were modified by grafting polymerization of polyfunctional monomer, pentaerythritol triacrylate (PETA), in the presence of 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane peroxide (DDHP) via melt extrusion. Fourier transform infrared spectroscopy (FTIR), melt strength test (MS), mechanical property test, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) were used to characterize the microstructure and properties of the modified composites. The crystallization kinetics was investigated by Mo method while apparent activation energy of crystallization of the composites was determined by Kissinger method. The FTIR results showed that the acrylic polymers were grafted onto the polypropylene chains. The grafting made the melt strengths and the mechanical properties of the modified composites, and the interfacial adhesion between PP and glass fiber all enhanced. High melting and crystallization temperatures, high crystallization rate and large activation energy of crystallization were also obtained after grafting. In addition, the grafted acrylic polymers recovered the depressed crystallization of polypropylene and restrained α-β transition in fatigue experiment.     

Polypropylene/natural rubber composites filled with recycled newspaper: Effect of chemical treatment using maleic anhydride‐grafted polypropylene and 3‐aminopropyltriethoxysilane

A study on effect of chemical treatment using maleic anhydride‐grafted polypropylene (MAPP) and 3‐aminopropyltiethoxysilane (3‐APE) was investigated. The performance of the MAPP and 3‐APE were investigated by means of torque development, mechanical properties, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy morphology, and water absorption. The results revealed that the use of MAPP or 3‐APE in the composites has increased the stabilization torque, tensile strength, Young's modulus, water absorption, and thermal stability of the PP/NR composites. The incorporation of MAPP in the composites shows higher stabilization torque, tensile strength, E_B, Young's modulus, and lower water uptake when compared with the use of 3‐APE in the PP/NR composites. TGA and DSC results indicated that primary and secondary peak of DTG curve, initial degradation temperature (T₀), degradation temperature (T_deg), melting temperature (T_m), heat of fusion of composites (ΔH_f(com)), crystallinity of composites (X_PP), and PP (X_PP) increased, while total weight loss and thermal degradation rate decreased for both treated composites. The MAPP‐treated RNP‐filled PP/NR composites were found to be more thermal resistance and more crystalline than 3‐APE‐treated filled PP/NR RNP composites. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Radical grafting of polar monomers onto polypropylene by reactive extrusion

Polypropylene (PP) was functionalized in the melt by grafting polar monomers using an internal mixer and a corotating twin‐screw extruder. 2,5‐Bis(tertbutylperoxy)‐2,5‐dimethylhexane (Luperox 101) and dicumyl peroxide (DP) were the used radical initiators. The polar monomers were itaconic acid (IAc), 2‐octen‐1‐ylsuccinic anhydride (OY), 2‐hydroxyethyl methacrylate (HEMA), and 3‐allyloxy‐1,2‐propanediol (AP). Grafting was quantified by FTIR combined to Elemental Analysis. Grafting degree depends mainly on monomer and initiator natures and concentrations. Grafting degree maxima were 3.9, 2, 9.5, and 3.9 wt %, respectively, for IAc, OY, HEMA, and AP. Some properties of the modified PP were evaluated. Thermal analysis indicated that the polarity of PP increased by grafting reaction and size‐exclusion chromatography showed that the grafting was not accompanied by a significant M_w and viscosity decrease. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of nucleation and growth mechanisms on the heat deflection temperature of a reactively processed polypropylene nanocomposite

The development of a reactively processed polypropylene nanocomposite (PPNC) with consequential improvements in the heat deflection temperature (HDT), Vicat softening temperature (VST), and crystallization peak temperature (T_c) is reported herein. Neat PP without nanoclay was also reactively processed to elucidate the effects of fillers on the improvement in physical properties. The results show a considerable improvement in the HDT of PPNC (77.9 °C) compared to those of neat PP (62.6 °C) and reactively processed branched PP (BPP; 69.2 °C). Moreover, the T_c of PP in PPNC improved by ~14% compared to that of neat PP. Various models of nonisothermal crystallization kinetics were employed to elucidate the nucleation and crystal growth mechanisms, and to correlate them with the observed HDT improvement in PPNC. Thermal transitions investigated by modulated differential scanning calorimetry explained the changes observed in the VSTs of all the samples. To the best of our knowledge, this is the first report on a significant improvement in HDT along with a marked increase in Tc. Such simultaneous improvements in HDT, VST, and T_c are highly desirable for applications involving the use of PP-based materials in rigid packaging.     

Effect of zeolite 5A on the crystalline behavior of polypropylene (PP) in PP/β‐nucleating agent system

The effect of zeolite 5A on the crystalline behavior of polypropylene (PP) in PP/β‐nucleating agent system was investigated with X‐ray diffractometer (XRD), differential scanning calorimeter (DSC), and polarized light microscope (PLM) in this study. Zeolite 5A has less effect on crystalline phase of PP/β‐nucleating agent than does n‐CaCO₃, which is ascribed to the stronger surficial polarity and better dispersibility of zeolite 5A. The data of DSC indicated that the crystallization peak temperature of PP increases by 8.3°C in the presence of zeolite 5A, and n‐CaCO₃ increases 5.7°C in PP/TMB‐5 system, relative to pure PP. And the initial crystallization temperature (T_c0) and the relative crystallinity (X_c) of PP is much more dramatically raised in the presence of zeolite 5A than CaCO₃. The efficiency of zeolite 5A in reducing the spherulites size of PP was seen clearly from the PLM photographs. The mechanical testing results showed that the flexural strength and impact strength of PP/β‐nucleating agent system increased in the presence of zeolite 5A. POLYM. COMPOS., 2008. © Society of Plastics Engineers     

Synergistic effect of SBS and trimethylopropane trimethacrylate (TMPTMA) on dynamically vulcanized SEBS/PP blends

The SEBS/PP thermoplastic vulcanizates (TPVs) were prepared by melt blending. Di‐tert‐butyl peroxide (DTBP) was used as the curing agent in combination with trimethylopropane trimethacrylate (TMPTMA) and poly(styrene‐b‐butadiene‐bstyrene) (SBS) as the coagents for the curing process. The synergistic effect of TMPTMA and SBS on the structure and properties of TPVs was studied by means of FT‐IR, DSC, torque rheometer, and universal testing machine. Both SEBS and PP crosslinked and the network structure formed under the participation of TMPTMA and SBS. Compared with the sole addition of the coagent, simultaneous loading of both TMPTMA and SBS could provide the TPVs with better solvent‐resistance and excellent mechanical properties. The crosslinking mechanism of the TPVs was also proposed. The slight lower value of T_m for the TPVs indicated the improved miscibility between PP and SEBS due to the crosslinking reaction. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44392.