Grafting modification and properties of polypropylene with pentaerythritol tetra-acrylate

The α-β transition of isotactic polypropylene (PP) under stress hasn’t received much attention although it may cause deterioration of mechanical properties. PP was modified by grafting polyfunctional monomer, pentaerythritol tetra-acrylate (PETeA) carried out in a Haake mixer at 180 °C in the presence of 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane peroxide (DDHP) to enhance the melt strength and suppress formation of β crystal and α-β transition. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-rays diffraction (XRD), polarized optical microscopy (POM) and melt flow index (MFI) were used to characterize the microstructure and properties of the grafted PPs. The FTIR spectra and transient torque results indicated that the acrylic polymers were grafted onto the polypropylene chains. The grafted polypropylenes gave both high crystallization and melting temperatures, and lowered the spherulite dimensions, and increased the melt strength. The grafted branching polyacrylics retarded segmental chain movement during processing and seemed to recover the depression in fatigue experiment to some extent. This work will be benefit to the extensional processing and especially provide the information on the fatigue stability of crystal structure of isotactic polypropylene during the engineering application.     

反应性相容剂的制备及其在PP/玻璃纤维复合材料中的应用

以马来酸酐(MAH)为接枝单体、丙烯酸-2-羟乙酯为共聚单体,利用熔融接枝技术对聚丙烯(PP)进行改性;以MAH/丙烯酸-2-羟乙酯熔融接枝改性PP为相容剂,研究相容剂对PP/玻璃纤维复合材料结构和性能的影响。结果表明:与未接枝PP相比,熔融接枝PP分子上接枝了MAH和—OH基团,而且熔融接枝反应对PP的熔点和热稳定性具有明显影响。另外,随着接枝PP含量的增加,PP/玻璃纤维复合材料的力学性能明显改善。当接枝PP含量为15%时,复合材料的拉伸强度提高了32%,冲击强度提高了13%,表明采用熔融共接枝工艺制备的PP具有优良的增容、偶联和分散效果。     

Mechanical properties and fracture morphology of Al(OH)3/polypropylene composites modified by PP grafting with acrylic acid

Al(OH)₃/polypropylene (PP) composites modified by polypropylene grafted with acrylic acid (FPP) were prepared by melt extrusion. Effect of PP grafting with acrylic acid on mechanical properties and fracture morphology of Al(OH)₃/polypropylene composites were investigated. Although incorporation of Al(OH)₃ reduced the mechanical properties of PP, addition of FPP increased the mechanical properties of Al(OH)₃/PP composites. It is suggested that addition of FPP improve the dispersion of Al(OH)₃ and the interfacial interaction between filler and matrix. Mechanical properties of Al(OH)₃/FPP/PP composites depend on the grafting rate and the content of FPP. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2617–2623, 2001     

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     

Performance of long glass fiber‐reinforced polypropylene composites at different injection temperature

Long glass fiber‐reinforced polypropylene composites were prepared using self‐designed impregnation device. Effects of the different injection temperature on mechanical properties, crystallization, thermal, and dynamic mechanical properties of long glass fiber‐reinforced polypropylene composites were discussed. The differential scanning calorimetry (DSC) results indicate that the melting peak temperature of PP/LGF composites gradually reduced, however, the crystallinity of PP/LGF composites gradually increased with increasing injection temperature. Thermo‐gravimetric analyzer (TGA) results demonstrate that with increasing injection temperature, the temperature of the PP/LGF composites melt increased, the viscosity of the PP/LGF composites melt lowered, the mold filling of the PP/LGF composites melt was easy, the shear force of glass fiber was relatively low, which made the residual length of glass fiber in products increase. Dynamic thermal mechanical analyzer (DMA) results show that the storage modulus of PP/LGF composites is the highest while the injection temperature is at 290°C, and the peak value of tan σ of PP /LGF composites at 290°C is minimal, which indicates that the mechanical properties of PP /LGF composites at 290°C is the best. What' more, the injection temperature at 290°C significantly ameliorated “glass fiber rich skin” of products of glass fiber‐reinforced composites. J. VINYL ADDIT. TECHNOL., 24:233–238, 2018. © 2016 Society of Plastics Engineers     

玻璃纤维增强煤基抗冲共聚聚丙烯的性能

采用双螺杆挤出共混法制备了短玻璃纤维(GF)改性聚丙烯(PP)2240S的共混物,通过力学性能分析测试、扫描电子显微镜表征、熔体流动速率测试和熔融结晶分析等研究了改性体系的力学性能、显微结构、加工流动性和结晶性能等。结果表明,当GF添加量为30%时,复合体系的弯曲强度、弯曲弹性模量、拉伸强度等较纯PP分别提高约112%,269%和108%,但GF与基体粘结力弱导致冲击强度没有提高;为进一步改善界面作用力,以5%马来酸酐接枝聚丙烯作相容剂,相同GF添加量下PP的弯曲强度达86.99 MPa,弯曲弹性模量达5073 MPa,拉伸强度达78.5 MPa,简支梁缺口冲击强度达14.78 kJ/m2,比纯PP的相关指标分别提高约161%,302%,190%和131%,GF与PP界面粘结力增强,PP的力学性能随GF含量的递增而大幅提高。但GF降低了PP的熔体流动速率,并且体系的结晶温度基本未变,结晶度降低,可能与未产生界面横晶有关。     

Reinforcement of polypropylene using sisal fibers grafted with poly(methyl methacrylate)

Sisal fiber (SF) surface modification was carried out by grafting with methyl methacrylate (MMA) using cerium and ammonium nitrate as initiator. The effects of reaction time, monomer, and initiator concentration on the grafting parameters were systematically investigated. The results showed that MMA was successfully grafted onto the sisal fiber surface. The PMMA‐grafted sisal fibers were melt blended with polypropylene (PP) and then injection molded. The PP/SF composites were characterized by means of thermal analysis, mechanical testing, wide‐angle X‐ray diffraction, and SEM examination. PMMA grafted onto the surface of SF enhanced the intermolecular interaction between the reinforcing SF and PP matrix, improved the dispersion of SF in the PP matrix, and promoted the formation of β‐crystalline PP. These enhanced the thermal stability and mechanical properties of PP/SF composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1055–1064, 2003     

Interfacial interaction in AI(OH)3/polypropylene composites modified by insitu‐functionalized polypropylene

To investigate the interfacial interaction of AI(OH)₃/polypropylene (PP) composites modified by in situ‐functionalized polypropylene (FPP), AI(OH)₃/polypropylene (PP) composites containing a low AI(OH)₃ content, modified by in situ‐grafted acrylic acid, were prepared by a one‐step melt‐extrusion process. The effect of in situ FPP on the crystallization and melting behavior, crystalline morphology of the composites, and interfacial interaction between the filler and PP was investigated. The crystallization and melting behavior and crystalline morphology of PP in the composites depended upon the interfacial physical [heterogeneous nucleation of AI(OH)₃; cocrystallization and compabilitization of PP with in situ FPP] and the interfacial chemical interaction between both the components in the composites. FTIR results indicated that there exists a chemical reaction between AI(OH)₃ and in situ FPP. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 110–120, 2002; DOI 10.1002/app.10270     

The effect of epoxy and tetramethyl thiuram disulfide on melt‐grafting of maleic anhydride onto polypropylene by reactive extrusion

In this report, melt grafting of maleic anhydride (MAH) and epoxy resin onto polypropylene (PP) by peroxide‐initiated reactive extrusion has been investigated. As evidenced by Fourier transform infrared spectroscopy, both MAH and epoxy resin were successfully grafted onto PP through the reactions of MAH with PP and epoxy resin with MAH. It was found that tetramethyl thiuram disulfide could promote the grafting of MAH and inhibit the degradation of PP, as revealed by chemical titration and melt flow experiments, through prolonging the lifetime of the macroradical; meanwhile, epoxy resin could reduce the sublimation of MAH and the maximum grafting degree of MAH. Furthermore, the introduction of grafted products was found to enhance the mechanical properties of PP/glass fiber composites, and this influence was very significant at high grafting degrees with a high content of epoxy resin, which could be interpreted in terms of improved compatibility and adhesion at the interface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43422.     

Interfacial effects in polypropylene–silica nanocomposites

Grafted inorganic nanoparticles can greatly improve the mechanical performance of polymers. To examine the effects of the interfacial characteristics generated by the grafting polymer bonded to nanoparticle surfaces, we chemically grafted nano‐silica with different polymers and then melt‐mixed it with polypropylene (PP). We extracted the homopolymers produced during the graft polymerization from the grafted products before the composites were manufactured to get rid of the side effects of the nongrafting polymers. We tailored the interfacial interaction between the grafted nano‐SiO₂ and PP matrix by changing the amount of the grafting polymers on the nanoparticles, that is, the grafting percentage. Mechanical tests indicated that all the composites incorporated with grafted nano‐SiO₂ particles possessed much higher impact strength than untreated SiO₂/PP composites and neat PP. The greatest contribution of the particles was made at a low grafting percentage. Tensile measurements showed that the treated nanoparticles could provide PP with stiffening, strengthening, and toughening effects at a rather low filler content (typically 0.8 vol %) because of the enhanced interfacial adhesion resulting from molecular entanglement and interdiffusion between the grating polymers on the nanoparticles and matrix macromolecules. The presence of grafting polymers on the nanoparticles provided the composites with a tailorable interphase. The tensile performance of the composites was sensitive to the nature of the grafting polymers. Basically, a hard interface was beneficial to stress transfer, whereas a soft one hindered the development of cavities in the matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1771–1781, 2004     

丙烯酸接枝聚丙烯的制备及其结构与性能

综述近年来国内外关于丙烯酸接枝聚丙烯(PP—g—AA)的制备方法,主要包括熔融接枝、固相接枝、辐射接枝、光引发接枝、悬浮接枝、溶液接枝和复合材料中的原位接枝法等,以及各种制备工艺和条件对接枝率的影响;并对PP—g—AA的结构与性能尤其是接枝丙烯酸后聚丙烯的结晶与熔融行为进行了详细阐述。     

PP-g-(MAH-St)对PP/木粉复合材料力学性能的影响

在聚丙烯中(PP)中添加马来酸酐(MAH)和共单体苯乙烯(St),通过熔融挤出法制备了高接枝率的PP-g-(MAH-St),红外光谱分析证明了St和MAH成功接枝到PP主链上。研究了PP-g-(MAH-St)对PP/木粉复合材料力学性能的影响,并用扫描电镜观察了复合材料冲击断面的微观形貌。结果表明,与现有PP-g-MAH相比,只要添加少量PP-g-(MAH-St)就能有效改善PP/木粉复合材料的界面相容性,从而提高材料的力学性能;PP-g-(MAH-St)中MAH的接枝率对复合材料力学性能影响显著,当MAH接枝率为2.8 %时,能使木塑复合材料力学性能达到最佳。     

Physical properties of PP-g-AA prepared by melt extrusion and its effects on mechanical properties of PP

Polypropylene grafting with acrylic acid, PP-g-AA (FPP), was prepared by melt extrusion. The physical properties of FPP and effect of FPP on mechanical properties of polypropylene (PP) were investigated. Experimental results showed that an increase in the grafting rate of FPP resulted in an increase in the crystallization peak temperature, melt peak temperature, and degree of crystallization of PP. Double melting peaks were observed for OPP prepared by adding dicumyl peroxide into PP and FPP with low grafting rate due to the degradation of PP. As the grafting rate was increased, the double melt peaks converted into a single melt peak. It is suggest that FPP with higher grafting rate resulted in enhanced nucleation and crystallization ability of PP. The grafting of AA onto the PP chain improved the thermal stability and mechanical properties of PP materials. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2609–2616, 2001     

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.     

Nonisothermal crystallization kinetics of polypropylene‐layered double hydroxide composites: Correlation with morphology

In this work the effect of nanofiller on nonisothermal crystallization behavior of composites based on polypropylene (PP) was investigated by differential scanning calorimetry. The materials were prepared by melt mixing. Both an alkyl sulfonate salt modified layered double hydroxide (LDH) and an unmodified LDH were used as nanofillers and both PP and PP/polypropylene grafted with maleic anhydride (PP‐g‐MA) blend were used as matrices. The morphology of composites was investigated by X‐ray diffraction and transmission electron microscopy. No exfoliation was noticed in all prepared composites, but the hybrid materials showed an intercalated structure. The thermal properties and crystallization behavior were studied by conventional differential scanning calorimetry. In particular, the kinetic crystallization parameters were obtained using the modified Avrami equation for a nonisothermal process, whereas the activation energy of the global crystallization process was estimated using the Kissinger equation. The Avrami parameters suggest a significant effect on the crystallization of PP for the composites containing both the organically modified LDH and PP‐g‐MA. The results indicate a complex crystallization process of PP and evidence that the crystallization process can not be only explained by intercalation phenomenon, but the constrain effect ofpolymer chains on the filler surface and/or betweenthe filler clusters should play a significant role. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Physical and mechanical properties of Al(OH)3/polypropylene composites modified by in situ‐functionalized polypropylene

Al(OH)₃/polypropylene (PP) composites modified by in situ‐functionalized polypropylene (FPP) were prepared by a one‐step melt‐extrusion process. The effect of in situ FPP on the crystallization and melting behavior, melt‐flow index, limiting oxygen index, thermal degradation, mechanical properties, and fracture morphology of Al(OH)₃/PP composites was studied. Formation of in situ FPP resulted in a decreased crystallization temperature and melting point of PP in the composites, an increased melt‐flow index, and improved tensile and flexural strengths of Al(OH)₃/PP composites, whereas the thermal degradation behavior and limiting oxygen index was not been influenced. The impact strength of the Al(OH)₃/PP composites modified by in situ FPP depended upon the content of the initiator, dicumyl peroxide, and the monomer, acrylic acid. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2850–2857, 2002; DOI 10.1002/app.10269     

Polymerization compounding composites of nylon‐6,6/short glass fiber

Nylon‐6,6 was grafted onto the surface of short glass fibers through the sequential reaction of adipoyl chloride and hexamethylenediamine onto the fiber surface. Grafted and unsized short glass fibers (USGF) were used to prepare composites with nylon‐6,6 via melt blending. The glass fibers were found to act as nucleating agents for the nylon‐6,6 matrix. Grafted glass fiber composites have higher crystallization temperatures than USGF composites, indicating that grafted nylon‐6,6 molecules further increase crystallization rate of composites. Grafted glass fiber composites were also found to have higher tensile strength, tensile modulus, dynamic storage modulus, and melt viscosity than USGF composites. Property enhancement is attributed to improved wetting and interactions between the nylon‐6,6 matrix and the modified surface of glass fibers, which is supported by scanning electron microscopy (SEM) analysis. The glass transition (tan δ) temperatures extracted from dynamic mechanical analysis (DMA) are found to be unchanged for USGF, while in the case of grafted glass fiber, tan δ increases with increasing glass fiber contents. Moreover, the peak values (i.e., intensity) of tan δ are slightly lower for grafted glass fiber composites than for USGF composites, further indicating improved interactions between the grafted glass fibers and nylon‐6,6 matrix. The Halpin‐Tsai and modified Kelly‐Tyson models were used to predict the tensile modulus and tensile strength, respectively.     

A reactive extrusion process for the free radical grafting of silanes onto polypropylene: Effects of processing conditions and properties of water cross‐linked silane‐grafted polypropylene

Silane grafting and water cross‐linking of polypropylene (PP) are a recent method to modify its properties, such as melt strength, heat, and chemical resistance. This work aims at grafting silanes onto PP by reactive extrusion. The occurrence of the grafting of silane onto PP was confirmed by Fourier transform infrared (FTIR) and a method based on FTIR was developed to quantify the amount of polymerized silane and that of silane grafted onto PP. The molar mass of the silane‐grafted PP and its melt viscosity were also measured. A multiobjective optimization strategy was used to study the effects of processing conditions on the quality of the silane‐modified PP. It was concluded that to maximize the amount of silane grafted on PP and minimize the amount of polymerized silane and the decrease in PP chain scission, screw speed and barrel temperature should be low and feed rate high. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Effects of clay contents on the dynamic mechanical and rheological properties of polypropylene/MAH‐g‐POE/clay composites

A series of polypropylene/maleic anhydride grafted polypropylene octane elastomer (MAH‐g‐POE)/clay (PPMC) nanocomposites were prepared with a novel compatilizer MAH‐g‐POE and different contents of octadecyl amine modified montmorillonite, and the effects of clay contents on the dynamic mechanical and rheological properties of these PPMC composites were investigated. With clay content increasing, the characteristic X‐ray diffraction peak changed from one to two with intensity decreasing, indicating the decreasing concentration of the intercalated clay layers. The gradual decrease of crystallization temperature of PPMC composites with the increase of clay loading should be attributed to the preferred intercalation of MAH‐g‐POE molecules into clay interlayer during blending, which is also reflected by scanning electron microscopy observations. By evaluating the activation energy for the glass transition process of MAH‐g‐POE and polypropylene (PP) in the PPMC composites, it is found that clay intercalation could cause the restriction effect on the glass transition of both MAH‐g‐POE and PP, and this restriction effect appears stronger for PP and attained the highest degree at 5 wt % clay loading. The melt elasticity of PP could be improved apparently by the addition of MAH‐g‐POE, and 5 wt % clay loading is enough for further enhancing the elastic proportion of PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polypropylene‐organoclay nanocomposite: Preparation,microstructure, and mechanical properties

A series of polypropylene (PP) nanocomposites containing 2, 4, and 6 wt % of an organophilic montmorillonite clay was prepared via direct melt mixing in the presence of maleic anhydride grafted polypropylene (PP‐g‐MAH) as compatibilizing agent. Microstructure characterization was performed by X‐ray diffraction analysis. Nanocomposites exhibited a 15 and 22% enhancement in tensile modulus and impact strength, respectively. The heat deflection temperature of PP nanocomposites was 36°C greater than for pure PP. Thermal and mechanical properties of nanocomposites were compared to properties of traditional PP‐talc and PP‐glass fiber composites. The results showed that the properties of nanocomposites improved compared to ordinary polypropylene composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009