Characterization of high melt strength propylene/1-butene copolymer synthesized by in situ heat induction melt reaction

Propylene/1-butene copolymer powders were produced through bulk copolymerization of propylene with 1-butene in a 12 m³ polymerization reactor. High melt strength polypropylene (HMSPP) was synthesized by in situ heat induction melt reaction, in which pure propylene/1-butene copolymer powders without any additives were used as a basic resin and trimethylolpropane triacrylate (TMPTA) as a crosslinking agent. The structure and properties of the resultant HMSPP were characterized by means of various measurements. The content of TMPTA strongly influenced the melt strength and melt flow rate (MFR) of HMSPP. With increasing the content of TMPTA, the melt strength of HMSPP increased, and the MFR reduced. In addition, owing to the existence of crosslinking structure, thermal stability and tensile strength of HMSPP were improved compared with pristine propylene/1-butene copolymer. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

高熔体强度聚丙烯的研制

用过氧化物引发聚丙烯(PP)交联制备高熔体强度聚丙烯(HMSPP),研究了过氧化物的用量、反应温度、螺杆转速对HMSPP性能的影响。得到的HMSPP比普通PP的熔体强度提高约3倍。用所研制的HMSPP进行发泡实验,制得泡孔结构较均匀且闭孔的发泡制品。     

加工参数及配方对PP/LLDPE共混物泡孔形态的影响

采用高压毛细管流变仪对不同含量碳酸钙(CaCO3)的聚丙烯/线型低密度聚乙烯(PP/LLDPE)共混物的流变性能进行了表征;并利用自制的实验装置,在不同发泡温度和饱和压力下,对共混物进行了超临界CO2模拟挤出发泡实验研究。结果表明:使用高熔体强度聚丙(烯HMSPP)发泡可以获得较好的泡孔形态;添加成核剂CaCO3可以使发泡试样的泡孔结构更加规则,泡孔分布更加均匀;随着CaCO3含量的增加,共混物的稠度上升,非牛顿指数降低,当CaCO3含量为3%时,共混物的发泡效果较好;130℃为最佳发泡温度,此时发泡试样的结构完整尺,寸均匀;随着饱和压力的增加发,泡试样的泡孔密度也有所提高。     

用于发泡成型的高熔体强度聚丙烯的研究

在同向双螺杆挤出机上,对聚丙烯(PP)进行硅烷交联,制得高熔体强度聚丙烯(HMSPP),然后制备高发泡倍率的PP制品。分析了改性剂用量对PP熔体流动速率、熔体黏度、熔体强度、凝胶含量、力学性能、热性能和发泡性能的影响。结果表明:自制HMSPP的熔体强度和熔体黏度分别是纯PP的5.01倍和1.52倍,力学性能和耐热性与纯PP相比均有较大提高,可用于成型高发泡倍率制品。     

PP/LDPE blends produced by reactive processing. I. Grafting efficiency and rheological and high‐elastic properties of [PP/LDPE]‐g‐IA melts

Itaconic acid (IA) was grafted onto polypropylene/low‐density polyethylene (PP/LDPE) blends. The ratio of polymeric components was varied from 100 : 0 to 0 : 100. The effect of the variation in the ratios of the components on grafting efficiency and concomitant side processes was studied. Grafting of IA (1 wt %) was initiated by 2,5‐dimethyl‐2,5‐di(tert‐butyl peroxy)‐hexane (0.3 wt %) and was carried out in an extruder reactor equipped with a dynamic mixer. An increase in the PP content of the blend led to a lower yield of the grafted product. With low concentrations of LDPE in the blend (up to 25 wt %), grafting efficiency was observed to increase, and this increase was greater in comparison with the additive rule. Between 25 and 99 wt % of LDPE in the blend, grafting efficiency rose monotonically with LDPE concentration. At or below an LDPE content of 25 wt %, the melt flow index (MFI) of [PP/LDPE]‐g‐IA would increase unlike with PP‐g‐IA systems. But a small quantity of PP (below 25 wt %) in the [PP/LDPE]‐g‐IA blends would result in a decreased MFI unlike with LDPE‐g‐IA. The dependence of swell index and melt strength on the ratio of polymeric components in [PP/LDPE]‐g‐IA blends also was investigated. ©2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5095–5104, 2006     

高熔体强度聚丙烯树脂的结构与性能

采用差示扫描量热法、傅里叶变换红外光谱、毛细管流变、熔体拉伸等方法,从结晶性、黏弹性及物理机械性能等方面对高熔体强度聚丙烯(HMSPP)树脂进行结构表征与性能分析。结果表明:HMSPP树脂具备较高的弯曲模量,同时具备优异的抗熔垂能力和更宽的加工温度;拉伸黏度随拉伸速率的增大而增大,呈现出HMSPP应变硬化这一明显行为,使得熔体在热成型过程中具有均匀变形的自我调节能力,从而克服普通聚丙烯在热成型加工中的严重熔垂问题;含有较长接枝链段的HMSPP树脂在刚性、熔体强度、结晶性能等方面均优于普通聚丙烯。     

Microcellular foaming of PE/PP blends

Three different polyethylene/polypropylene (PE/PP) blends were microcellular foamed and their crystallinities and melt strengths were investigated. The relationship between crystallinity, melt strength, and cellular structure was studied. Experimental results showed that the three blends had similar variation patterns in respect of crystallinity, melt strength, and cellular structure, and these variation patterns were correlative for each blend. For all blends, the melt strength and PP melting point initially heightened and then lowered, the PP crystallinity first decreased, and then increased as the PE content increased. At PE content of 30%, the melt strength and PP melting point were highest and the PP crystallinity was least. The blend with lower PP crystallinity and higher melt strength had better cellular structure and broader microcellular foaming temperature range. So, three blends had best cellular structure at PE content of 30%. Furthermore, when compared with PE/homopolymer (hPP) blend, the PE/copolymer PP (cPP) blend had higher melt strength, better cellular structure, and wider microcellular foaming temperature range, so it was more suited to be microcellular foamed. Whereas LDPE/cPP blend had the broadest microcellular foaming temperature range because of its highest melt strength within three blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4149–4159, 2007     

Super‐toughed polymer blends derived from polypropylene random copolymer and ethylene/styrene interpolymer

In this article, blends of polypropylene random copolymer (PP‐R) with a novel impact modifier, namely ethylene/styrene interpolymer (ESI), were prepared to evaluate the effectiveness of ESI in toughening PP‐R and the influence of ESI content on the mechanical, thermal, and rheological properties of polymer blends. Results showed that super‐toughened PP‐R/ESI blends (ca. Izod impact strength ≥ 500 J/m) were readily achieved with only 5 wt % ESI. The blends exhibited significant improvement in both impact strength and elongation, while small loss in tensile strength and elastic modulus when increasing ESI content. ESI had a nucleating effect that caused PP matrix to crystallize at higher temperatures, whereas PP‐R/ESI blends presented lower melting temperatures (T_m) than PP‐R matrix and T_m decreased with the increment of ESI content. Rheology study indicated that both PP‐R matrix and PP‐R/ESI blends presented shear thinning behaviors during melt processing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reactive extrusion of PP/natural rubber blends

Reactive extrusion of polypropylene (PP)/natural rubber (NR) (90/10) blends was conducted in the presence of a peroxide [1,3-bis(t-butylperoxy)benzene] and coagent (trimethylolpropanetriacrylate, TMPTA). Effects of peroxide and coagent content were studied in terms of melt index (MI), melt viscosity, morphology, thermal, and mechanical properties. At a constant content of the coagent, melt viscosity increased at a low and decreased at a high content of the peroxide. On the other hand, melt viscosity increased monotonically with the coagent concentration at constant peroxide content. The increase and decrease of viscosity were interpreted in terms of crosslinking and chain scission of PP, which governed the rubber domain size and mechanical properties of the reactive blends. © 1995 John Wiley & Sons, Inc.     

Dynamically cured polypropylene/epoxy blends

The dynamic vulcanization process, usually used for the preparation of thermoplastic elastomers, was used to prepare polypropylene (PP)/epoxy blends. The blends had crosslinked epoxy resin particles finely dispersed in the PP matrix, and they were called dynamically cured PP/epoxy blends. Maleic anhydride grafted polypropylene (MAH‐g‐PP) was used as a compatibilizer. The effects of the reactive compatibilization and dynamic cure were studied with rheometry, capillary rheometry, and scanning electron microscopy (SEM). The crystallization behavior and mechanical properties of PP/epoxy, PP/MAH‐g‐PP/epoxy, and dynamically cured PP/epoxy blends were also investigated. The increase in the torque at equilibrium for the PP/MAH‐g‐PP/epoxy blends indicated the reaction between maleic anhydride groups of MAH‐g‐PP and the epoxy resin. The torque at equilibrium of the dynamically cured PP/epoxy blends increased with increasing epoxy resin content. Capillary rheological measurements also showed that the addition of MAH‐g‐PP or an increasing epoxy resin content increased the viscosity of PP/epoxy blends. SEM micrographs indicated that the PP/epoxy blends compatibilized with PP/MAH‐g‐PP had finer domains and more obscure boundaries than the PP/epoxy blends. A shift of the crystallization peak to a higher temperature for all the PP/epoxy blends indicated that uncured and cured epoxy resin particles in the blends could act as effective nucleating agents. The spherulites of pure PP were larger than those of PP in the PP/epoxy, PP/MAH‐g‐PP/epoxy, and dynamically cured PP/epoxy blends, as measured by polarized optical microscopy. The dynamically cured PP/epoxy blends had better mechanical properties than the PP/epoxy and PP/MAH‐g‐PP/epoxy blends. With increasing epoxy resin content, the flexural modulus of all the blends increased significantly, and the impact strength and tensile strength increased slightly, whereas the elongation at break decreased dramatically. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1437–1448, 2004     

化学改性高熔体聚丙烯的制备及其挤出发泡特性研究

以过氧化二异丙苯(DCP)为交联剂、三烯丙基异三聚氰酸酯(TAIC)为助交联剂,通过平行双螺杆挤出机制备了高熔体强度聚丙烯(HMSPP),研究了DCP用量对PP的流变性能、材料的热性能及发泡特性的影响。结果表明:DCP与TAIC配合使用能有效控制PP交联,从而制得有一定凝胶含量的HMSPP,同时材料的耐热性也得以提高,当DCP用量为0.8份,TAIC为3份时,制备的HMSPP,挤出发泡特性最佳。     

Development of nanofibrous morphology in LDPE/LLDPE/PP blends and its effect on mechanical properties of blend films

Nanofibrous morphology has been observed in ternary blends of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and isotactic polypropylene (PP) when these were melt‐extruded via slit die followed by hot stretching. The morphology was dependent on the concentration of the component polymers in ternary blend LDPE/LLDPE/PP. The films were characterized by wide angle X‐ray diffraction (XRD), scanning electron microscopy (SEM), and testing of mechanical properties. The XRD patterns reveal that the β phase of PP is obtained in the as‐stretched nanofibrillar composites, whose concentration decreases with the increase of LLDPE concentration. The presence of PP nanofibrils shows significant nucleation ability for crystallization of LDPE/LLDPE blend. The SEM observations of etched samples show an isotropic blend of LDPE and LLDPE reinforced with more or less randomly distributed and well‐defined nanofibrils of PP, which were generated in situ. The tensile modulus and strength of LDPE/LLDPE/PP blends were significantly enhanced in the machine direction than in the transverse direction with increasing LLDPE concentration. The ultimate elongation increased with increasing LLDPE concentration, and there was a critical LLDPE concentration above which it increased considerably. There was a dramatic increase in the falling dart impact strength for films obtained by blow extrusion of these blends. These impressive mechanical properties of extruded samples can be explained on the basis of the formation of PP nanofibrils with high aspect ratio (at least 10), which imparted reinforcement to the LDPE/LLDPE blend. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel multimonomer‐grafted polypropylene preparation and application in polypropylene/poly(vinyl chloride) blends

A novel grafted polymer was prepared in one step through free‐radical melt grafting in a single‐screw extruder. It was shown that the addition of styrene (St) to the melt‐grafting system as a comonomer could significantly enhance the grafting degree of methyl methacrylate (MMA) onto polypropylene (PP) and reduce the degradation of the PP matrix by means of Fourier transform infrared and melt flow rate testing, respectively. Then, the potential of using multimonomer‐grafted PP, which was designated PP‐g‐(St‐co‐MMA), as the compatibilizer in PP/poly(vinyl chloride) (PVC) blends was also examined. In comparison with PP/PVC blends, the average size of the dispersed phase was greatly reduced in grafted polypropylene (gPP)/PVC blends because of the addition of the PP‐g‐(St‐co‐MMA) graft copolymer. The tensile strength of the gPP/PVC blends increased significantly, and the impact strength was unchanged from that of the pure PP/PVC blends. The results of differential scanning calorimetry and scanning electron microscopy suggested that the compatibility of the PP/PVC blends was improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of dynamically cured PP/MAH‐g‐EVA/epoxy blends

A method concerning with the simultaneous reinforcing and toughening of polypropylene (PP) was reported. Dynamical cure of the epoxy resin with 2‐ethylene‐4‐methane‐imidazole (EMI‐2,4) was successfully applied in the PP/maleic anhydride‐grafted ethylene‐vinyl acetate copolymer (MAH‐g‐EVA), and the obtained blends named as dynamically cured PP/MAH‐g‐EVA/epoxy blends. The stiffness and toughness of the blends are in a good balance, and the smaller size of epoxy particle in the PP/MAH‐g‐EVA/epoxy blends shows that MAH‐g‐EVA was also used as a compatibilizer. The structure of the dynamically cured PP/MAH‐g‐EVA/epoxy blends is the embedding of the epoxy particles by the MAH‐g‐EVA. The cured epoxy particles as organic filler increases the stiffness of the PP/MAH‐g‐EVA blends, and the improvement in the toughness is attributed to the embedded structure. The tensile strength and flexural modulus of the blends increase with increasing the epoxy resin content, and the impact strength reaches a maximum of 258 J/m at the epoxy resin content of 10 wt %. DSC analysis shows that the epoxy particles in the dynamically cured PP/MAH‐g‐EVA/epoxy blends could have contained embedded MAH‐g‐EVA, decreasing the nucleating effect of the epoxy resin. Thermogravimetric results show the addition of epoxy resin could improve the thermal stability of PP, the dynamically cured PP/MAH‐g‐EVA/epoxy stability compared with the pure PP. Wide‐angle x‐ray diffraction analysis shows that the dynamical cure and compatibilization do not disturb the crystalline structure of PP in the blends. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A new method for producing high melt strength polypropylene with reactive extrusion

A high‐melt‐strength polypropylene (HMSPP) was prepared using a twin‐screw reactive extruder from a commercial isotactic polypropylene through two stages, first, maleic anhydride is grafted to polypropylene to obtain a maleic anhydride‐grafted polypropylene (PP‐g‐MA), and then the grafted polymer is reacted with epoxy to extend the branched chain. Fourier transformed infrared spectroscopy indicated that maleic anhydride was grafted on polypropylene and reacted with epoxy. Melt flow rate and sag resistance test showed that the melt strength of the HMSPP improved considerably. Differential scanning calorimetry test showed that the long chain branches (LCBs) act as a nucleating agent in the crystallization of the HMSPP, which leads to a high crystallization temperature and crystallinity. Furthermore, the LCB efficiency of the HMSPP can also be calculated by analyzing its rheological property. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

高熔体强度聚丙烯/低密度聚乙烯共混体系的挤出发泡行为研究

利用熔体流动速率测试仪和转矩流变仪对不同比例的高熔体强度聚丙烯(HMSPP)/低密度聚乙烯(PELD)共混体系的流变行为进行研究,并对共混体系的流变数据进行分析.随后采用超临界CO2作为发泡剂进行了HMSPP/PE-LD共混体系的挤出发泡研究,并通过真密度计和扫描电子显微镜表征了发泡材料的表观密度和泡体结构参数.结果表...     

LDPE共混改性PP的结晶行为及模压发泡效果

采用单螺杆挤出机制备了低密度聚乙烯(LDPE)共混改性聚丙烯(PP)可发性粒料,并通过模压发泡工艺得到改性PP发泡材料;考察了发泡剂的热分解特性以及LDPE的含量对共混体系的熔融/结晶行为、晶体结构和发泡性能的影响。结果表明:与纯偶氮二甲酰胺(AC)相比,复合发泡剂的分解温度下降了45℃;LDPE的引入没有改变PP的晶型结构,但降低了共混体系的结晶度;当LDPE的含量为15%～20%时,LDPE/PP共混体系的发泡效果最佳。     

The effect of compatibilizers and organically modified nanoclay on the morphology and performance properties of poly(acrylonitrile–butadiene–styrene)/polypropylene blends

In this study, poly(acrylonitrile–butadiene–styrene)/polypropylene (ABS/PP) blends with various compositions were prepared by melt intercalation in a twin‐screw extruder. Modifications of the above blends were performed by using organically modified montmorillonite (OMMT, Cloisite 30B) reinforcement as well as two types of compatibilizers, namely polypropylene grafted with maleic anhydride (PP‐g‐MAH) and ABS grafted with maleic anhydride (ABS‐g‐MAH). Increasing the PP content in ABS matrix seems to increase the melt flow and thermal stability of their blends, whereas a deterioration of the tensile properties was recorded. On the other hand, the addition of ABS to PP promotes the formation of the β‐crystalline phase, which became maximum at 30 wt% ABS concentration, and increases the crystallization temperature (T_c) of PP. A tendency for increase of T_c was also recorded by incorporation of the above compatibilizers, whereas the glass transition temperature (T_g) of PP and SAN phase in ABS was reduced. Regarding the Young's modulus, the greatest improvement was observed in pure ABS/PP blends containing organically modified nanoclay. However, in reinforced pure PP, the use of compatibilizers is recommended in order to improve the elastic modulus. The addition of OMMT to noncompatibilized and compatibilized ABS/PP blends significantly improves their storage modulus. POLYM. ENG. SCI., 56:458–468, 2016. © 2016 Society of Plastics Engineers     

Modification of Ethylene Propylene Diene Terpolymer Rubber by Some Thermoplastic Polymers

Abstract

Blends of ethylene propylene diene terpolymer (EPDM) rubber with thermoplastic polyolefins such as low‐density polyethylene (LDPE), high‐density polyethylene (HDPE), high molecular weight polypropylene (PP), and polypropylene random copolymer grade (PP‐R) were prepared by melt mixing. The physico‐mechanical properties, equilibrium swelling in benzene, and aging properties of the binary blends were investigated, analyzing the effect of the rubber/thermoplastics ratio and the type of the thermoplastic material on these properties. The data obtained indicate that EPDM/PP‐R blend in 20/80 w/w% shows the highest physico‐mechanical properties with improved retained tensile strength at 90°C for 7 days. This blend ratio also gives excellent retained equilibrium swelling in benzene at room temperature for 7 days, although EPDM/LDPE blend in 80/20 w/w% imparts the highest retained elongation at break at 90°C for 7 days.     

反应挤出制备高熔体强度PP

采用反应挤出方法制备高熔体强度聚丙烯,通过凝胶渗透色谱仪、差示扫描量热仪、偏光显微镜等研究了改性产品的结构与性能,并进行挤出发泡应用实验。结果表明：采用特殊的过氧化物引发剂和支化促进剂,与聚丙烯基础树脂共混后通过双螺杆挤出机熔融连续反应挤出,可以直接制备具有长链支化结构的聚丙烯,熔体强度提高300％;挤出发泡试样泡孔均匀,发泡倍率达到50倍,具有较好的可发性能。