Influence of Coagents on the Silane Grafting and Cross-linking of Polypropylene

The grafting of vinyltrimethoxysilane (VTMS) onto polypropylene (PP) was carried out in a melt process, and the cross-linking in the hot water. The influence of coagents, i.e., styrene (St), divinylbenzene (DVB), triallyl isocyanurate (TAIC) and trimethylolpropane triacrylate (TMPTA) on the grafting degree, gel percentage, melt flow index (MFI) of the VTMS modified PP were investigated. It was found that the incorporation of the coagents influenced the grafting and cross-linking of VTMS. The crystallization behavior and crystal structure of the coagent assisted VTMS-cross-linked PP were studied by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WXAD), respectively. The thermogravimetric analysis (TG) studies indicate that the thermal stability of VTMS-cross-linked PP was improved by the incorporation of coagents.     

Structure and properties of dynamically cured EPDM/PP blends

The structure and properties of polyolefin blends of ethylene–propylene–diene terpolymer (EPDM) and polypropylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured with PP under shear with dicumyl peroxide (DCP) at different shear conditions (blend–cure). Blends were also prepared for comparison from EPDM which were dynamically cured in the absence of PP and blended later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastic composition were studied. In blend–cure, the melt viscosity increased with increasing DCP concentration in blends of 75% EPDM and 25% PP, but it decreased with increasing DCP concentration in blends of 75% PP and 25% EPDM. In cure–blend, however, the melt viscosity increased with increasing DCP concentration for all compositions. The melt viscosity decreased with increasing intensity of the shear mixing presumably due to the formation of the smaller segregated microdomain of the crosslinked EPDM gels in both blend–cure and cure–blend materials. The crystallization rate was higher in EPDM/PP blends than in PP homopolymer. The crystallization rates for various blending conditions were also compared.     

高模量弹性体对PP结晶行为及力学性能的影响

应用DSC和力学性能测试研究了PP/OTE、PP/EPDM共混物的结晶行为和它们的增韧作用。结果表明 ,烯烃类热塑性弹性体 (以下简称OTE)对PP的结晶性能无明显影响 ,EPDM对PP成核速率有促进作用。PP/OTE在赋予PP较好低温韧性的同时 ,使共混物的刚性得以适度兼顾 ,且易于加工。PP/OTE共混体系的综合性能优于PP/EPDM共混物     

聚丙烯/三元乙丙橡胶共混体系的研究

研究了三元乙丙橡胶（ＥＰＤＭ）对聚丙烯（ＰＰ）结晶行为的影响以及ＰＰ／ＥＰＤＭ共混物的形态与性能的关系。ＥＰＤＭ对ＰＰ的熔点、结晶温度无明显影响,ＰＰ／ＥＰＤＭ共混物的结晶度随ＥＰＤＭ组份含量的增加而降低,适量的ＥＰＤＭ可使ＰＰ的晶体尺寸减小,晶胞参数与组份比无关。当ＥＰＤＭ用量为３０％～４０％时,共混物的冲击强度迅速提高。     

The effect of addition of different elastomers upon the crystalline nature of PP

Thermal and morphological studies have been performed on polymer blends based on ethylene–octene copolymer (PEE)/PP and ethylene–propylene–diene copolymer (EPDM)/PP. The thermal and morphological behavior of PEE, EPDM, PEE/PP, and EPDM/PP systems were analyzed by differential scanning calorimetry (DSC) and polarizing light microscopy, respectively. It was observed that the behaviors of crystallization kinetics of PEE/PP and EPDM/PP blends were similar. It was also observed that addition up to 10–20% (w/w) of elastomers resulted in increasing of spherulite size. The heat of fusion (ΔH_f) and crystallinity degree of PEE/PP and EPDM/PP systems decreased when the elastomer contents were increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3530–3537, 2001     

Preparation and characterization of vinyltrimethoxysilane and dicumyl peroxide–cured (ethylene propylene diene monomer)/polypropylene thermoplastic vulcanizates

The present investigation deals with understanding the influence of vinyltrimethoxysilane (VTMS) concentration on the mechanical, thermal, thermomechanical, rheological, morphological, gel content, crosslinking density, and compression set properties of dynamically vulcanized ethylene propylene diene monomer (EPDM)/polypropylene (PP) (60/40, w/w) ‐based thermoplastic vulcanizates. It was determined that the values of crosslinking density, gel content, tensile strength, Young's modulus, elongation at break, and viscosity increased; whereas that of compression set, melting temperature, enthalpy of melting, crystallinity, and damping factor decreased with increased addition of VTMS in the EPDM/PP‐based thermoplastic vulcanizate. This is attributed to the physical crosslinking caused because of VTMS grafting on EPDM and chemical crosslinking induced by VTMS between PP and EPDM. This has been confirmed by Fourier‐transform infrared spectroscopy spectra, whereas the thermomechanical and scanning electron microscopy analysis confirmed increased compatibility between EPDM and PP on the addition of VTMS. J. VINYL ADDIT. TECHNOL., 23:312–320, 2017. © 2015 Society of Plastics Engineers     

Mechanical properties,morphological structure,and thermal behavior of dynamically photocrosslinked PP/EPDM blends

A dynamically photocrosslinked polypropylene (PP)/ethylene–propylene–diene (EPDM) rubber thermoplastic elastomer was prepared by simultaneously exposing the elastomer to UV light while melt‐mixing in the presence of a photoinitiator as well as a crosslinking agent. The effects of dynamic photocrosslinking and blend composition on the mechanical properties, morphological structure, and thermal behavior of PP/EPDM blends were investigated. The results showed that after photocrosslinking, tensile strength, modulus of elasticity, and elongation at break were improved greatly. Moreover, the notched Izod impact strength was obviously enhanced compared with corresponding uncrosslinked blend. Scanning electron microscopy (SEM) morphological analysis showed that for uncrosslinked PP/EPDM blends, the cavitation of EPDM particles was the main toughening mechanism; whereas for dynamically photocrosslinked blends, shear yielding of matrix became the main energy absorption mechanism. The DSC curves showed that for each dynamically photocrosslinked PP/EPDM blend, there was a new smaller melting peak at about 152°C together with a main melting peak at about 166°C. Dynamic mechanical thermal analysis (DMTA) indicated that the compatibility between EPDM and PP was improved by dynamic photocrosslinking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3371–3380, 2004     

降解PP/EPDM共混物的结晶性能研究

采用过氧化二异丙苯(DCP)降解聚丙烯(PP),熔融法制备了降解PP与三元乙丙橡胶(EPDM)共混物,采用差示扫描量热分析(DSC)及广角X射线衍射(WAXD)研究了降解PP/EPDM共混物的结晶行为,结果发现PP降解后β-PP晶型(300)消失 ;降解PP/EPDM共混物的非等温结晶过程是由成核控制的,并伴有明显的快速初级结晶和缓慢的次级结晶过程,降解PP以均相成核的三维球晶方式生长.     

PP/EPDM热塑性弹性体结晶与熔融行为研究

采用动态光交联法制备了PP／EPDM[聚丙烯／（乙烯／丙烯／二烯）共聚物]热塑性弹性体。运用广角X射线衍射（WAXD），偏光显微镜（POM）与差示扫描量热仪（DSC）对PP的结晶形态及结晶与熔融行为进行表征。结果表明，EPDM的加入妨碍PP形成完善的球晶，而动态光交联体系中PP的球晶更不完善；动态光交联对PP的结晶温度及熔点影响不大，结晶度低于未交联体系的。     

高极性PP熔融接枝物的制备及应用

采用复合引发体系、双组分熔融接枝法 ,研制开发了高极性聚丙烯接枝物。讨论了复合引发体系、共聚单体在接枝过程中的作用 ,研究了接枝物对PP/EPDM的相容性的影响。将少量接枝物与PP、EPDM、HDPE共混 ,并添加相容剂及其他助剂 ,可得到高冲击性能、可涂装性能优良的汽车保险杠材料 ,其性能达到国外同类产品指标要求     

Thermal and crystallization behavior of silane‐crosslinked polypropylene

Silane‐crosslinked polypropylene (PP) has been prepared first by the grafting of silane onto the backbone of PP in a melt process and then by crosslinking in warm water. The effects of type and concentration of silane and peroxide on the silane grafting on PP were investigated. The thermal behavior of the silane‐crosslinked PP was studied by thermogravimetric (TG) and differential scanning calorimetry (DSC) methods. TG results show that PP prepared via silane crosslinking increases its thermal stability greatly. It has been found from DSC measurements that the crystallization temperatures, ie the onset temperature and peak temperature of the exotherm of the silane‐crosslinked PP, increase compared with those of the pure PP. The silane crosslinking hardly changes the crystallinity degree of PP. The crystallization behavior of the silane‐crosslinked PP was also studied by wide‐angle X‐ray diffraction analysis. Copyright © 2004 Society of Chemical Industry     

PET/PC blends: Effect of chain extender and impact strength modifier on their structure and properties

Methylene diphenyl diisocyanate (MDI) affects the morphology, rheological, mechanical, and relaxation properties, as well as tendency to crystallize of PET in PET/PC/(PP/EPDM) ternary blends produced by the reactive extrusion. Irrespective of the blend phase structure, the introduction of MDI increases the melt viscosity (MFI dropped), resulting from an increase in the molecular weight of the polymer chains; the PET crystallinity was also reduced. MDI favors compatibility of PET with PC in PET/PC/(PP/EPDM) blends. This is explained by intensified interphase interactions on the level of segments of macromolecules as well as monomer units. The presence of MDI causes a substantial rise in the dynamic shear modulus within the high‐elastic region of PET (for temperature range between T_g,PET and that of PET cold crystallization); the processes of PET cold crystallization and melt crystallization become retarded; the glass‐transition temperatures for PET and PC become closer to each other. MDI affects insignificantly the blend morphology or the character of interactions between the disperse PP/EPDM blend and PET/PC as a matrix. PP/EPDM reduces the intensity of interphase interactions in a PET/PC/(PP/EPDM), but a rise in the degree of material heterogeneity. MDI does not change the mechanism of impact break‐down in the ternary blends mentioned above. Increased impact strength of MDI‐modified materials can be explained by higher cohesive strength and resistance to shear flow at impact loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of interface reactions in compatibilised ground tyre rubber polypropylene elastomeric alloys

Abstract

Compounds of ground tyre rubber (GTR) and polypropylene (PP) were prepared in an internal mixer and characterised by means of mechanical, thermal and morphological testing. Only physical melt mixing could not provide a suitable interface compatibilisation and leads to compounds with poor mechanical properties. However, the application of a reactive melt mixing process, using organic peroxides as radical donators, was found to be suitable to initiate a compatibilisation reaction via interphase grafting. These compatibilised GTR/PP elastomeric alloy (EA) systems exhibit interesting mechanical properties which are close to that of conventional two phase thermoplastic elastomers (TPE) based on dynamically vulcanised ethylene propylene diene monomer (EPDM)/PP blends. Results of the morphology investigations substantiate the occurrence of a compatibilisation reaction between rubber particles and PP matrix during reactive mixing which is most probably responsible for the enhanced material properties of the GTR/PP EA.     

动态硫化对三元乙丙橡胶/聚丙烯共混体系等温结晶行为和形态结构的影响

研究了三元乙丙橡胶/聚丙烯(EPDM/PP)共混物和动态硫化EPDM/PP热塑性弹性体(TPV)的等温结晶行为及形态结构,并用Avrami方程对其进行等温结晶动力学分析。结果表明,EPDM/PP共混物和EPDM/PP TPV的等温结晶行为符合Avrami方程,在相同的结晶温度下,TPV比共混物的Avrami指数小,半结晶时间短,结晶速率常数大;EPDM/PP共混物为双连续相结构,而EPDM/PP TPV是以硫化的细小橡胶颗粒为分散相、PP为连续相的"海-岛"结构,橡胶颗粒尺寸约为0.5μm。     

The effect of polypropylene/polyamide 66 blending modification on melt strength and rheologic behaviors of polypropylene

Common linear polypropylene (PP) was modified by blending with polyamide 66 (PA66) under the act of compatibilizer in a twin-screw extruder in an attempt to improve the melt strength (MS) of PP. The MS of pure PP and modified PPs were measured by MS testing unit at three temperature of 190, 210, and 230 °C, and the MS improvement of PP was verified. The MS of the modified PPs increased with increasing the content of PA66. The steady- and dynamic-shear rheological behaviors of pure PP and modified PPs were investigated using a capillary rheometer and a parallel-plate rotating rheometer. The steady-shear rheological analysis results revealed that modified PPs had higher melt shear viscosity, stronger non-Newtonian behaviors, and higher zero shear-rate viscosity. The dynamic-shear rheological analysis showed modified PPs had higher melt complex modulus and smaller phase angle, which indicated that the melt viscosity and melt elasticity of PP were also enhanced. The modified PPs was characterized by DSC. DSC results revealed that the PA66 phase and PP phase of the modified PPs were in state of crystallization. The enhancement of MS, melt viscosity, and melt elasticity of modified PPs could be due to undisaggregated PA66 crystallization phase within the melt of PP blends.     

Polypropylene/polypropylene‐grafted acrylic acid blends for multilayer films: Preparation and characterization

Polypropylene (PP) was functionalized with acrylic acid (AA) and styrene (st) as a comonomer by means of a radical‐initiated melt‐grafting reaction. FTIR, ESCA, and ¹H‐NMR spectroscopies were used to characterize the formation of polypropylene grafted with acrylic acid (PP‐g‐AA) and polypropylene grafted with acrylic acid and styrene (PP‐g‐AAst). The content of AA grafted onto PP was determined by using volumetric titration. Blends of PP with 0–100 wt % of PP‐g‐AA were prepared by melt mixing. The effect of the modified polymer content on the surfaces of cast films was characterized through FTIR–ATR and ESCA analysis as well as contact‐angle, wetting‐tension, and ink‐adhesion measurements. The influence of the content of AA on the melting and crystallization temperature of PP was investigated by DSC. The contact angles of water on cast‐film surfaces of PP/PP‐g‐AA blends decreases with increasing modified polymer content and decreasing PP‐g‐AA molecular weight. A notorious improvement on wetting tension was observed with increasing modified polymer content and decreasing PP‐g‐AA molecular weight. From FTIR–ATR and ESCA spectra of the blends, a calculation was made of the carbonyl index on the films' surfaces. It was found that the higher the carbonyl index, the lower the contact‐angle value for the polypropylene blends. An increase in crystallization temperature of PP was observed when AA monomers were grafted into PP and with increasing PP‐g‐AA content in the blend, probably caused by a nucleation effect of AA monomers that would improve the crystallization capability of PP. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1497–1505, 2001     

Preparation and Properties of PB-1/PP Blends

Crystallization behavior, dynamic mechanical properties, mechanical properties and rheological properties of isotactic polybutene-1/polypropylene (PB-1/PP) blends prepared by melt-blending the two components through Brabender extruder were mainly studied via POM, DSC, DMA, capillary rheometer and so on, respectively. The results indicated that after adding PP in PB-1: size of the spherical crystal and degree of crystallization of PB-1 in the blends decreased, its melt temperature and crystallization temperature unchanged; tensile property of the blends was decreased, but impact and flexural properties were improved; change of the melt viscosity of the blends with the shear rate was more sensitive than pure PB-1.     

Crystallization kinetics of thermoplastic elastomeric blends based on ground tyre rubber

This work analyzes the crystallization process of thermoplastic elastomeric blends (TPE) based on ground tyre rubber (GTR). More specifically it analyzes the effect of GTR and fresh rubber materials, like ethylene propylene diene monomer (EPDM) and ethylene propylene rubber (EPR), on the crystallization of binary and ternary polypropylene (PP)‐based blends. The crystallization kinetics is studied under isothermal and nonisothermal conditions using differential scanning calorimetry (DSC). The kinetic parameters derived from the Avrami model are used to study the effect of temperature and rubber materials on the nucleation mechanism, the morphology of the crystalline structures, and the crystallization rate. Results reveal that GTR has a strong nucleating effect on PP and that its presence leads to higher crystallization rates. The EPDM presence has a slight effect on the PP crystallization process whereas EPR has no significant effect. From the DSC curves it is possible to detect an inverse relationship between temperature and the crystallization rate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42589.     

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.     

Mechanical property and morphology comparison between the two blends poly(propylene)/ethylene‐propylene‐diene monomer elastomer and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer

The comparison of the mechanical properties between poly(propylene)/ethylene‐propylene‐diene monomer elastomer (PP/EPDM) and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer [PP/MEPDM (MAH‐g‐EPDM)] showed that the latter blend has noticeably higher Izod impact strength but lower Young's modulus than the former one. Phase morphology of the two blends was examined by dynamic mechanical thermal analysis, indicating that the miscibility of PP/MEPDM was inferior to PP/EPDM. The poor miscibility of PP/MEPDM degrades the nucleation effectiveness of the elastomer on PP. The observations of the impact fracture mode of the two blends and the dispersion state of the elastomers, determined by scanning electron microscopy, showed that PP/EPDM fractured in a brittle mode, whereas PP/MEPDM in a ductile one, and that a finer dispersion of MEPDM was found in the blend PP/MEPDM. These observations indicate that the difference in the dispersion state of elastomer between PP/EPDM and PP/MEPDM results in different fracture modes, and thereby affects the toughness of the two blends. The finer dispersion of MEPDM in the blend of PP/MEPDM was attributed to the part cross‐linking of MEPDM resulting from the grafting reaction of EPDM with maleic anhydride (MAH) in the presence of dicumyl peroxide (DCP). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2486–2491, 2002