Polypropylene/polyamide 6/polypropylene-g-maleic anhydride blending monofilaments: effects of quench temperature

We describe the effects of quench temperature on the structure and mechanical properties of polypropylene/polyamide 6/polypropylene grafted maleic anhydride (PP/PA6/PP-g-PAH) blend monofilaments. The monofilaments were prepared by melt-spinning under different quench temperatures. The thermal properties were investigated by Differential scanning calorimetry (DSC) and the morphologies were observed using Scanning electron microscope (SEM). We measured the tensile strength, the loop strength, and the elongation at break of the monofilaments. Results demonstrated that the quench temperature had strong effects on the structure and mechanical properties of the PP/PA6/PP-g-MAH blend monofilaments. With the decrease of quench temperature, the tensile strength and the loop strength of the blend monofilaments increased obviously, which could be attributed to the different crystallization processes and orientation structures induced by changing quench temperatures.     

Modification of polypropylene with maleic anhydride: Ultrasonic irradiation effects

The mechanochemical reaction of modificated of polypropylene (PP) with maleic anhydride (MAH) has been studied by ultrasonic irradiation as an energy source at 60°C. Through 2³ factorial experimental design, three variables and their interactions were studied: the percentage of MAH, the percentage of benzoyl peroxide (BPO), and ultrasonic irradiation intensity (Watts). According to the results, an increase of wt % of MAH gave a negative effect in the grafting yield; in addition, this negative effect was observed in the interaction of MAH : BPO at a high range of wt %, this behavior is attributed to the homopolymerization of MAH at the experimental conditions employed. The higher positive effect onto the grafting yield was observed for the variable watts (ultrasonic irradiation intensity), even at low intensity. The better interaction of variables gave a MAH grafting degree of 4.65 wt % (93% yield). In addition, the effect of ultrasonic irradiation on the number-average molar mass (M_n), weight-average molar mass (M_w), and polydispersity index (M_w/M_n) was measured. It was observed that the M_w decreased 13.73% and the M_w/M_n also decreased by 11.98%. The o observed effect was attributed to the degradation mechanism induced by the ultrasound, which consists in the generation of macroradicals and their recombination. The product PP-g-MAH was characterized by infrared spectroscopy, also was used to prepare polypropylene–nylon-6 blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:45–52, 1998     

The reaction of polypropylene with maleic anhydride

An addition reaction of maleic anhydride with polypropylene takes place in the presence of radical reagents or sunlight. The initial rate of the reaction was proportional to the concentration of polypropylene and maleic anhydride, and one-half power of the concentration of the radical reagents. The increase in the temperature from 80 to 120°C increased the rate of the reaction and di-cumyl peroxide was effective as a radical reagent for this reaction. Ionic crosslinked rubber-like polymers were obtained from the reaction of maleic polypropylene with some alkali metal compounds. They showed the characteristic absorption band due to ? COO^? in their infrared spectra.     

Maleic anhydride grafting of polypropylene: peroxide and solvent effects

Abstract

The grafting of polyolefins with maleic anhydride (MA) has been incorporated into industrial practice to generate copolymers that can act as coupling agents between the non-polar polyolefins and different polar fillers and reinforcements. In the present study, two different peroxides were used to initiate the MA grafting onto polypropylene (PP), namely dicumyl peroxide (DCP) and 1,3-bis (terbutylisopropyl peroxi)benzene (DIBP). The use of DIBP allowed similar grafting yields to DCP to be obtained, but with less chain scission of the polyolefin. Moreover, the utilisation of a coagent, toluene (Tol), leads to a reduction in the chain scission of PP. A monotonous decrease in the melt flow index (MFI) of the polymer was observed with increasing molar ratio of Tol/MA, in the range of ratios considered (0–2·5). In addition, the free radical grafting of MA onto PP remained high and optimum grafting was obtained for a molar ratio Tol/MA of ～0·5. It was observed that the addition of toluene was effective, independent of the reaction process utilised, namely batch mixing or extrusion.     

Non-isothermal crystallization kinetic and compatibility of PTT/PP blends by using maleic anhydride grafted polypropylene as compatibilizer

The crystallization behaviors, non-isothermal crystallization kinetics, and the morphology of poly(trimethylene terephthalate)/Polypropylene (PTT/PP) blends using a maleic anhydride grafted polypropylene (PP-g-MAH) as a compatibilizer were investigated by differential scanning calorimeter (DSC) and scanning electron microscope (SEM), respectively. The results suggested that the blends exhibited different crystallization and melting behaviors due to different content of PP-g-MAH. All of the DSC curves of the blends exhibited two exothermic peaks and endothermic peaks. The commonly used Avrami equation modified by Jeziorny, Ozawa theory and the method developed by Mo were used, respectively, to fit the primary stage of non-isothermal crystallization process. The results suggested that the crystallization rate of PTT component was increased, whereas, that of PP component was retarded with the introduction of PP-g-MAH. The effective activation energy was calculated by differential iso-conversional method developed by Vyazovkin. The SEM result suggested that the introduction of PP-g-MAH greatly improved the compatibility between PTT and PP, and decreased the size of dispersed particles.     

Crystalline memory effects in isothermal crystallization of syndiotactic polypropylene

Isothermal crystallization behavior after partial or complete melting of syndiotactic polypropylene was investigated by differential scanning calorimetry (DSC). On partial melting, the total concentration of predetermined nuclei was found to decrease with increasing fusion temperature and increasing time period that the sample spent at a specific fusion temperature. A significant effect of the rate of heating to the fusion temperature was also observed. On complete melting, the total concentration of predetermined nuclei was found to approach a constant value, which is the concentration of infusible heterogeneous nuclei (e.g., impurities, catalyst residues) present originally in the sample. At a specific fusion temperature, the concentration of predetermined athermal nuclei was found to decrease exponentially with the time period spent in the melt. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 337–346, 2000     

Grafting of maleic anhydride onto polypropylene by reactive extrusion

Maleic anhydride grafting onto polypropylene was conducted in a twin‐screw extruder according to an experimental design in which the maleic anhydride and peroxide concentrations were varied. The modified polypropylene was characterized by FTIR spectroscopy, melt‐flow index measurements, size‐exclusion chromatography, differential scanning calorimetry, and nuclear magnetic resonance. The results showed that only the independent variable peroxide concentration influenced the amount of reacted maleic anhydride, whereas the two variables studied influenced the molecular weight of the grafted polypropylene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2706–2717, 2002     

Fractional crystallization of polypropylene

The development of a fractional crystallization technique for characterization of polypropylenes with respect to stereoregularity is described. It is a simple technique which is attractive for routine analysis and under suitable conditions yields quantitative data with good reproducibility. Separation by fractional crystallization from hot xylene solution is shown to take place according to polymer crystallizability and is relatively independent of molecular weight. It thus represents an alternative and in some ways superior approach to the more commonly used fractional extraction method. Preliminary work indicates that the fractional crystallization method may prove of value in establishing correlations between the stereoregular nature of polypropylenes and their physical properties.     

Maleic anhydride polypropylene modified cellulose nanofibril polypropylene nanocomposites with enhanced impact strength

Development of cellulose nanofibrils (CNFs) reinforced polypropylene (PP) nanocomposites using melt compounding processes has received considerable attention. The main challenges are to obtain well‐dispersed CNFs in the polymer matrix and to establish compatible linkages between the CNFs and PP. Manufacturing of CNF reinforced PP nanocomposites was conducted using a twin‐screw co‐rotating extruder with the masterbatch concept. Modifications of CNFs using maleic anhydride polypropylene were performed. The best mechanical properties of the nanocomposites are 1.94 GPa (tensile modulus), 32.8 MPa (tensile strength), 1.63 GPa (flexural modulus), 50.1 MPa (flexural strength), and 3.8 kJ m⁻² (impact strength), which represents about 36, 11, 21, 7, and 23% improvement, respectively, compared to those of pure PP (1.43 GPa, 29.5 MPa, 1.35 GPa, 46.9 MPa, and 3.1 kJ m⁻²). Fracture morphology examination indicated good dispersion of CNFs in the PP matrix was achieved through this specific manufacturing process. MAPP treatments enhanced the interfacial adhesion between the CNFs and PP. POLYM. COMPOS., 37:782–793, 2016. © 2014 Society of Plastics Engineers     

Interfacial tension of polypropylene/polystyrene: Degradation of polypropylene

The coefficient of the decrease of the interfacial tension of polypropylene/polystyrene with temperature is considerably higher than the value of other polymer pairs. This coefficient can be estimated by considering the change of the interaction parameters with temperature, but this approach fails for polypropylene/polystyrene, and other mechanisms are expected to play a role. In this paper it is shown that polypropylene starts to degrade at higher temperatures, leading to smaller polymer chains, which decrease the interfacial tension. Besides the change of the interaction parameters with temperature, these smaller molecules also contribute to the temperature coefficient, leading to an apparently high coefficient. The smaller molecules, however, lead to a permanent lower interfacial tension, e.g. the interfacial tension of polypropylene/polystyrene at 200°C is 4.9, 3.9, and 3.0 mN/m, if the polypropylene is first processed at 200, 250, and 300°C, respectively.     

Self-reinforcement of polypropylene by flow-induced crystallization during continuous extrusion

Self-reinforced polypropylene (PP) sheets have been prepared from melt flow-induced crystallization through a conical slit die fed by a conventional extruder. Their structure and properties, influenced by the die pressure ranging from 20 to 50 MPa and die outlet temperature, are studied by scanning electron microscopy observation, differential scanning calorimetry analyses, tensile strength, and light transmittance measurements. At a die outlet temperature of 162°C and a pressure above 30 MPa, conspicuous increases in the melting peak, tensile strength, and light transmittance (they can be used to characterize the self-reinforcement degree of sheet) are observed. The self-reinforcement degree, however, increases only slightly with increasing pressure as it exceeds 40 MPa. Raising the die outlet temperature from 162 to 172°C results in a further increase in the self-reinforcement degree (for example, a highest tensile strength of 288 MPa) while keeping the pressure at 40 MPa, so bulk PP materials with high properties can be produced from continuous melt extrusion under pressures lower than 40 MPa. Furthermore, the melt temperature plays an important role in determining the properties of self-reinforced polymeric materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2111–2118, 1998     

Isothermal crystallization kinetics and morphology development of isotactic polypropylene blends with atactic polypropylene

The crystallization kinetics and morphology development of pure isotactic polypropylene (iPP) homopolymer and iPP blended with atactic polypropylene (aPP) at different aPP contents and the isothermal crystallization temperatures were studied with differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscopy. The spherulitic morphologies of pure iPP and larger amounts of aPP for iPP blends showed the negative spherulite, whereas that of smaller amounts of aPP for the iPP blends showed a combination of positive and negative spherulites. This indicated that the morphology transition of the spherulite may have been due to changes the crystal forms of iPP in the iPP blends during crystallization. Therefore, with smaller amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends increased with increasing aPP and presented a lower degree of perfection of the γ form coexisting with the α form of iPP during crystallization. However, with larger amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends decreased and reduced the γ‐form crystals with increasing aPP. These results indicate that the aPP molecules hindered the nucleation rate and promoted the molecular motion and growth rate of iPP with smaller amounts of aPP and hindered both the nucleation rate and growth rate of iPP with larger amounts of aPP during isothermal crystallization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1093–1104, 2007     

The effects of alkaline earth dehydroabietate on the crystallization process of polypropylene

In this article, the influence of alkaline earth dehydroabietates, which were prepared from Na‐dehydroabietate, on crystallization of polypropylene (PP) from the melt state was studied by differential scanning calorimetry and polarization microscopy. It was found that magnesium dehydroabietate could improve mechanical properties and crystallization temperatures of PP and also decrease the size of spherulites. Kinetic analysis of PP isothermal crystallization showed that magnesium dehydroabietate decreased the fold surface energy of the developing crystals of PP and promoted the nucleation and crystallization of PP. However, calcium dehydroabietate increased the fold surface energy of the developing crystals of PP, but had no nucleation effect on PP. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2644–2651, 2002     

加入助剂的马来酸酐熔融接枝聚丙烯研究

用双螺杆挤出机研究了马来酸酐 (MAH)对聚丙烯 (PP)的自由基熔融接枝。采用正交试验优化了熔融接枝条件 ,系统研究了引发剂过氧化二异丙苯 (DCP)、单体MAH、助剂ABX用量对马来酸酐接枝率的影响 ,并对其影响因素作了分析。研究表明ABX助剂能降低PP降解 ,同时也提高了马来酸酐的接枝率。确定了较佳的原料配比为m(PP)∶m(MAH)∶m(DCP)∶m(ABX)=1 0 0∶4∶0 4∶0 35。     

A factorial design applied to polypropylene functionalization with maleic anhydride

Maleic anhydride functionalized PP was prepared in a melt-mixer according to a factorial design. Two levels of maleic anhydride concentration (MA), dicumyl peroxide concentration (DCP), reaction time, and temperature were employed. The isolated and interaction effects of these variables on the degree of functionalization and molecular weights were analyzed. The products were characterized by Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), titration, and torque measures. The reaction time showed no appreciable effect within the studied range (10 to 20 minutes); however, the other three factors showed significant main effects. MA and temperature presented an important interaction effect on the degree of functionalization and molecular weights. The highest degrees of functionalization were found to be related to the smallest molecular weights.     

Miscibility and crystallization of metallocene polyethylene blends with polypropylene

The crystallization and morphology of very‐low‐density polyethylene (VLDPE) and ultra‐low‐density polyethylene (ULDPE) blends with isotactic polypropylene (PP) were studied by differential scanning calorimetry (DSC) and hot‐stage optical microscopy (HSOM) with polarized light. In particular, the isothermal crystallization of PP in molten PE was investigated. A polypropylene homopolymer was melt‐blended with six types of VLDPEs and ULDPEs, with variations in branch content and length and in molecular weight. All the blends contained 20% PP by mass. It was found that the crystallization temperatures of PP and PE changed in the blends, and the crystallization of PP was affected by branch length and content and by the molecular weight of the PE, indicating a certain degree of miscibility between PP and PE. The isothermal crystallization rate of PP decreased in the blends; in particular, the crystallization rate of PP was slower in the ULDPE with lower MFI, suggesting that crystallization of PP was hindered by PE and that its rate was regulated by the viscosity of ULDPE. HSOM images showed that a portion of the PP crystallized from molten PE, although phase separation was obvious, providing additional information on the miscible behavior between PP and VLDPEs (or ULDPEs). Furthermore, the miscible level between the PP and the ULDPEs was higher than that between the PP and the VLDPEs because the degree of change in the crystallization behavior of the PP and PE was greater in the PP–ULDPE blends. This was possibly a result of the higher branch content in the ULDPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1179–1189, 2003     

Characteristics of cylindritic crystallization of polypropylene

Characteristics of cylindritic crystallization of polypropylene were studied by means of optical microscopy. It has been shown that a distinct structural memory effect is observed during the cylindritic crystallization. This memory effect can be attributed to thermal stability of row nuclei giving rise to the cylindritic crystallization. Negative or mixed type cylindrites are formed depending on the crystallization temperature (T_c > 410 and T_c < 410 K, respectively). Cylindrites obtained by stepwise crystallization are constructed of segments with different optical characteristics and melting points. Boundary lines of parabolic, hyperbolic, ellipsoidal or linear shape can be developed between the cylindrites and spherulites formed parallel. Equations describing the boundary lines are given in the present publication.     

苯乙烯对马来酸酐熔融接枝聚丙烯的影响

用双螺杆挤出机分别制备了马来酸酐(MAH)和MAH-苯乙烯(St)共单体接枝共聚聚丙烯(PP)。红外光谱分析表明:MAH单体被接枝到PP大分子链上;引入St后,产物熔体流动速率从16.42 g/10min降为0.60 g/10 min;吸光度比从0.021升高到0.778,但St含量过高时,PP基体发生交联,影响接枝共聚物的加工性能。探讨了共单体St的作用机理以及交联机理。     

聚丙烯复合材料的非等温结晶动力学

采用差示扫描量热仪研究了β成核剂和水滑石(LDH)/β成核剂复配的成核剂对聚丙烯(PP)非等温结晶动力学及熔融行为的影响。结果表明:加入成核剂后,PP中晶体分布不均匀且分散度增大。莫志深方法采用F(θ)表征聚合物在单位时间内达到某一结晶度时所需的冷却(或加热)速率,结晶度达到40%时,纯PP的F(θ)为3.82,加入β成核剂的PP的F(θ)为3.30,加入LDH/β成核剂的PP的F(θ)为2.49。与纯β成核剂相比,LDH/β成核剂能更好地提高PP的结晶温度、结晶速率,增强PP的β晶熔融峰,减弱β晶和α晶共存熔融峰和α晶熔融峰。