Antioxidant behaviour of a nanosilica-immobilized antioxidant in polypropylene

A nanosilica-immobilized antioxidant was prepared and incorporated into polypropylene (PP) by melt compounding. It has been found that the antioxidant efficiency of the nanosilica-immobilized antioxidant was superior to the corresponding low molecular counterpart (AO), based on the measurement of the oxidation induction time (OIT) of PP/nanosilica-immobilized antioxidant and PP/AO compounds containing an equivalent antioxidant component. By paying attention to the changes of carbonyl absorption and tensile strength of PP compounds with thermal oven aging time, it was observed that the thermal oxidative stability of PP/nanosilica-immobilized antioxidant was much higher than that of PP/AO compound during the long-term accelerated thermal aging.     

Antioxidant behavior of a novel sulfur-bearing hindered phenolic antioxidant with a high molecular weight in polypropylene

A novel sulfur-bearing hindered phenolic antioxidant with a molecular weight of 1305.9 (SAO) was successfully synthesized via thiol-acrylate Michael addition reaction and its structure was clarified by nuclear magnetic resonance (NMR) and fourier transform infrared spectra (FTIR). The short-term oxidation induction time (OIT) of polypropylene (PP) compounds obtained at 210 °C showed that the OIT value of SAO-containing PP was higher than that of PP using Chinox 1035 with a molecular weight of 642.9 as a stabilizer. Long-term accelerated thermal aging test of PP compounds in an air oven at 150 °C, however, exhibited that the aging resistance of SAO-stabilizing PP was inferior to that of 1035-containing PP, quite contrary to their respective short-term effect on PP stabilization. The possible reasons of this contradiction were discussed from the viewpoint of the antioxidants' molecular structure and the limitations of the OIT approach in lifetime prediction.     

Synthesis of a novel sulfur-bearing secondary antioxidant with a high molecular weight and its comparative study on antioxidant behavior in polypropylene with two commercial sulfur-bearing secondary antioxidants having relatively low molecular weight

A novel sulfur-bearing secondary antioxidant with a high molecular weight of 2252 (OS-POSS), successfully synthesized via photoinitiated thiol-ene click reaction, was compared with two commercial sulfur-bearing secondary antioxidants on the stabilization of polypropylene (PP). The results of their oxidation induction time (OIT) via differential scanning calorimeter measurement (DSC) showed that the higher the molecular weight of secondary antioxidant is, the longer the OIT value, whether such sulfur-bearing antioxidant is used singly or in combination with primary antioxidant. The study of their long-term accelerated thermal aging in the air oven at 150 °C displayed that the molecular structure of sulfur-bearing secondary antioxidant, besides molecular weight, is another highly important factor determining the antioxidant efficiency, i.e., physical loss of antioxidants with the relatively low molecular weight may determine antioxidant efficiency, whereas thioether groups having neighboring ester carbonyl moieties may decompose more hydroperoxides with quicker rate.     

Synthesis of 3,5-ditert-butyl-4-hydroxybenzoates and their thermal antioxidation behavior for polypropylene

Butyl 3,5-ditert-butyl-4-hydroxybenzoate (BB), octyl 3,5-ditert-butyl-4-hydroxybenzoate (OB), and dodecyl 3,5-ditert-butyl-4-hydroxybenzoate (DB) were synthesized and characterized, and their performance as antioxidant for polypropylene (PP) were also investigated. The thermooxidative stability of PP with different antioxidants were assessed by the measurements of long-term accelerated aging, differential scanning calorimetery, and thermogravimetric analysis. The results showed that 3,5-ditert-butyl-4-hydroxybenzoates could effectively inhibit the oxidation degradation of PP. And it was also found that the antioxidant efficiency of BB, OB, and DB for PP was in the order of DB > OB > BB.     

Phenolic prepreg waste as functional filler with antioxidant effect in polypropylene and polyamide-6

Milled phenol-formaldehyde glass-fibre scrap (prepreg) was mixed with polypropylene (PP) and polyamide-6 (PA6). The oxidation induction time (OIT) of PP/prepreg composite measured by both chemiluminescence (CL) and Differential Scanning Calorimetry (DSC) was significantly longer than the oxidation induction time of unstabilised base PP. In addition, mechanical testing showed that the prepreg filler stabilised both PP and PA6 towards oxidation during long-term accelerated ageing. Headspace-gas chromatography/mass spectrometry (HS-GC/MS) showed that PP/prepreg composites emit somewhat larger amounts of volatile compounds compared to the reference PP/glass fibre composites, while the amount of volatile components emitted from PA6/prepreg composites was similar to the reference PA6/glass fibre composites. The new prepreg composites could have potential in thermally demanding applications especially if a secondary phosphite stabiliser is added to further increase the oxidative stability through synergy effects.     

Structure effect of benzofuranone on the antioxidant activity in polypropylene

This work deals with the antioxidant activity of benzofuranone compounds in polypropylene (PP). The antioxidant activities of ten benzofuranone compounds in PP were compared using melt flow index (MFI) values of PP stabilized by benzofuranone compounds primarily. The results show: firstly, that the increase of electron donating ability of substituent in 3-substituted benzene ring is beneficial to the improvement of antioxidant activity. Secondly, it has been verified that the steric hindrance of 2′-position substituent can weaken the antioxidant activity of benzofuranone. But when 2′-position substituent forms a hydrogen bond with 3-position reactive hydrogen, the steric hindrance is offset efficiently. Finally, the methyl and tert-butyl groups in the 5 and 7-position of parent benzene ring do not affect the antioxidant activity of benzofuranone compounds in PP obviously.     

Study on the antioxidant activities of benzofuranones in melt processing of polypropylene

The antioxidant activities of four benzofuranones in melt processing of polypropylene (PP) have been investigated using multiple extrusions. The antioxidant activities of those four benzofuranones with different substituent groups have been evaluated using melt flow index (MFI) and yellowness index (Y.I.) of multiple-extruded PP stabilized with those antioxidants. The change of MFI values indicates as follows: firstly, the position of substituent group has a very important effect on the antioxidant activity of benzofuranone in the melt processing of PP i.e. methyl group of 2′-position may prevent the hydrogen donation of benzofuranone toward PP radicals and make the antioxidant activity of benzofuranone in PP decrease; secondly, electronic property of substituent group of para position to 3-reactive hydrogen has little influence on the antioxidant activity. Furthermore, the theory that the formation of antioxidative products due to the dimerization and disproportionation of benzofuranyl radicals is the main reason that induces the discoloration of stabilized PP has been predicted for the first time.     

Preparation and properties of POSS grafted polypropylene by reactive blending

The octavinyl polyhedral oligomeric silsesquioxane (POSS) grafted polypropylene (PP) was first prepared by reactive blending. The structure and properties of physical blending and reactive blending composites of PP/POSS were investigated by wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA). WAXD analysis shows that the POSS in the reactive blending composites has better compatibility with PP than in the physical blending composites. The β-form crystalline hence disappears even the non-reactive POSS can act as an effective β-nucleating agents. DSC analysis shows the reactive blending composites have higher crystalline temperature while POSS in the physical blending composites have little effect on the crystalline temperature. The modulus of reactive blending composites increases in the presence of POSS, while that of the physical blending composites decreases with increasing POSS content.     

具有环状结构的二氧化硅微聚集体的制备、表征及应用

通过溶胶-凝胶法制备二氧化硅溶胶,并采用喷雾干燥法对其进行形态调控.扫描电镜(SEM)结果表明,喷雾干燥使二氧化硅颗粒发生了形态重组,形成均匀的具有环状结构的二氧化硅微聚集体(PC16MS).通过熔融共混制备了二氧化硅/聚丙烯(PP)纳米复合材料,研究了PC16MS的加入对其微观结构、晶体结构、结晶行为、球晶形态、结晶成核密度和球晶生长速率等方面的影响.采用差示扫描量热(DSC)、偏光相差显微镜(POM)和广角X射线衍射(WAXRD)分析表明,在PP结晶初始阶段,PC16MS的加入大幅度提高了基体材料的成核密度,且使晶粒细化,缩短了结晶时间;当添加2%(质量分数)的PC16MS时,复合材料的结晶温度相对于纯PP提高了10.4℃,成核效率达到39.1%,优于大部分无机成核剂的成核效率.在相同条件下,添加2%未经过喷雾干燥处理的纳米二氧化硅(NC16MS),复合材料的结晶温度相对于纯PP提高3.26℃,成核效率达到12.3%.结果表明,喷雾干燥使二氧化硅颗粒发生了形态重组,形成的均匀介稳态微聚集体在熔融挤出过程中重新分散成纳米粒子,从而有效提高了二氧化硅作为成核剂的成核效率.     

Synergistic Effect of Phosphite with FuUerene C60 and Fullerenol C60（OH）24 as Antioxidants in Polypropylene

Polypropylene samples with fullerene C60, fullerenol C60（OH）24, 1010, C60/168, C60-OH/168 and 1010/168 as antioxidants were prepared by extrusions. MFR, YI, TGA and OIT of all the samples were tested. According to the results of MFR, during the melt extrusion, fullerene showed excellent stability effect on PP. The antioxidative ability of fullerene was comparable to the traditional antioxidant 1010. The antioxidative ability of fullerenol was not significant in the first extrusion and it accelerated the degradation of PP in the second and the third extrusions. TGA and OIT tests showed that the stability effects of fullerene and fullerenol were slightly lower than antioxidant 1010. In the first time, antioxidant 168 was reported to show great synergistic effects with fullerene and fullerenol as antioxidants, which sussested a simple way to enhance the antioxidative abilities of fullerene and fullerenol.     

Preparation of polypropylene/poly(styrene-co-(butyl methacrylate)) nanoblends by diffusion and subsequent copolymerization of monomers in isotactic polypropylene pellets

The diffusion and subsequent copolymerization of styrene(St)/butyl methacrylate(BMA) mixed monomers in i PP pellets to prepare copolymer nanoblends were investigated. The diffusion step was carried out at 90 ℃ for 2 h in water, and the copolymerization was initiated by the addition of BPO with the aid of a small amount of St. The diametrical distributions of both St and BMA units and their ratio St/BMA were investigated by micro FTIR. Both St and BMA can diffuse into the centres of i PP pellets. The diametrical distribution of St/BMA ratio is constant in all the copolymer blends. The copolymer composition depends on the comonomer feed ratio. The molecular weights of the copolymers were measured by GPC after extraction with tetrahydrofuran. The phase morphology of the copolymer blends was investigated by FESEM, showing the average particle sizes of less than 100 nm. DSC measurements show that the diffusion and subsequent copolymerization of St/BMA monomers only occur in the amorphous regions of i PP pellets.     

Geometry dependence of the elongation behavior of a polypropylene melt through a micro die

A series of rheological experiments was performed for a polypropylene (PP) melt to explore its elongation behavior through a capillary die. Using an advanced twin-bore capillary rheometer with dies measuring 1.0, 0.5, and 0.25 mm in diameter, the experiments were performed at 210, 220, and 230 °C. The results indicated that the temperature of the PP melt had a significant effect on its extensional viscosity. The different decreases in the extensional viscosity values in the tested dies revealed the geometry dependence of the extensional viscosity. In the case of PP in the 0.25 mm die at 210 °C, the extensional viscosity values under different extensional strain rates were much higher than those in the other dies. Only in the 1.0 mm die did the relationship between the extensional viscosity of PP and its temperature obey the Arrhenius equation due to the larger die size which related to a slight size effect on its elongation behavior. The calculated deviations of the extensional viscosity in the tested dies demonstrated that the increasing pressure applied to the PP melt in the micro channel was related to the geometry dependence of the elongation behavior of the PP melt. The change in the extensional viscosity eventually relied on the interaction of the die geometry, the temperature, and the extensional stress of the PP melt.     

Effect of the vibration shear flow field in capillary dynamic rheometer on the crystallization behavior of polypropylene

The self-made capillary dynamic rheometer was adopted to study the relationship between the crystallization behavior of isotactic polypropylene (iPP) and the vibration shear conditions, namely, vibration amplitude and vibration frequency. The crystalline structure of iPP under different vibration conditions was characterized by using differential scanning calorimeter (DSC) and wide-angle X-ray diffractometer (WAXD) techniques. The samples extruded under vibration shear conditions had a higher melting temperature (from DSC). A new shoulder-shape peak appeared at ca. 162 °C under low frequency or low amplitude conditions, which was engulfed by the main melting peak with the increase of the vibration amplitude or frequency. This was probably an indication that more perfect crystals had formed [Polym Eng Sci 38 (1998) 1-20]. The WAXD demonstrated that crystalline form of iPP extruded was not changed but the average crystalline size decreased, according to the Scherrer formula [Analytical methods of polymer materials, China Petrochemical Press, Beijing, 1997]. This proved a large increase in the number of small crystals.     

The effects of annealing in inert atmospheres and of oxygen concentration on chemiluminescence from polypropylene

It has been shown that heating polypropylene powder under a nitrogen atmosphere leads to the significant prolongation of the oxidation induction time measured by chemiluminescence in oxygen at 130 and 140 °C. While heating in nitrogen from 0 to 4 h at 140 °C leads to the linear increase of oxidation induction time, the maximum chemiluminescence intensity I_stat increases with the time of sample annealing until 2 h; then it starts to decay. The different and sometime unknown thermal history of the sample may thus explain the scatter of induction times of oxidation observed with different PPs whether they be pure or stabilised. Maximum chemiluminescence intensity plotted vs. concentration of oxygen in the surrounding atmosphere at 130 and 140 °C also increases linearly; however, this does not correspond with very small reduction of oxidation induction time. The four-parametric “master equations” used in our earlier papers were applied to fit the chemiluminescence runs both in oxygen and in nitrogen. The equation operates with the rate constants of hydroperoxide decomposition and oxidation spreading but at the same time, it takes into account the possible effect of oxidation products on decomposition of hydroperoxides.     

The effects of reprocessing cycles on the structure and properties of isotactic polypropylene/cloisite 15A nanocomposites

The effects of reprocessing cycles on the structure and properties of isotactic polypropylene (PP)/Cloisite 15A (OMMT) (5 wt. %) nanocomposites was studied in presence of maleic anhydride-grafted-polypropylene (PP-g-MA) (20 wt. %) used as the compatibiliser to improve the clay dispersion in the polymer matrix. The various nanocomposite samples were prepared by direct melt intercalation in an internal mixer, and further they were subjected to 4 reprocessing cycles. For comparative purposes, the neat PP was also processed under the same conditions. The nanocomposite structure and the clay dispersion have been characterized by wide angle X-ray scattering (WAXS), transmission electron microscopy (TEM) and rheological measurements. Other characterization techniques such as Fourier transform infrared spectroscopy (FT-IR), tensile measurements, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) have also been used to evaluate the property changes induced by reprocessing. The study showed through XRD patterns that the repetitive reprocessing cycles modified the initial morphology of PP/OMMT nanocomposites by improving the formation of intercalated structure, especially after the fourth cycle. Further, the addition of PP-g-MA promoted the development of intercalated/exfoliated silicate layers in the PP matrix after the second cycle. These results are in agreement with TEM observations indicating an improved silicate dispersion in the polymer matrix with reprocessing cycles displaying a morphology with both intercalated/exfoliated structures. The initial storage modulus (G′) of the nanocomposites, which was highly improved in presence of PP-g-MA seems to be less affected by reprocessing cycles at very low frequencies exhibiting a quasi-plateau compared to pristine PP/OMMT and PP. In contrast, the complex viscosity was found to decrease for the whole samples indicating that the main effect of reprocessing was a decrease in the molecular weight. Moreover, the thermal and mechanical properties of the nanocomposites were significantly reduced after the first cycle; nevertheless they remained almost unchanged during recycling. No change in the chemical structure was observed in the FT-IR spectra for both the nanocomposites and neat PP samples after 4 cycles.     

Interactions between the components in isotactic polypropylene blended with EPDM

The interaction of isotactic polypropylene with ethylene propylene diene terpolymer in their blends has been investigated by use of differential scanning calorimetry, dynamic mechanical analysis, wide- and small-angle x-ray scattering, and by investigating the nucleation and kinetics of crystallization of the iPP component under the polarization microscope. It is found, that the dispersion of the EPDM component in the iPP matrix is dependent on blend composition and is maximal at 10% EPDM content. An interface layer between the two components is formed by migration of iPP molecules into the EPDM phase. A model for this interface is proposed.     

A facile and green preparation of nanosilica-supported antioxidant and its reinforcement and antioxidation effect on styrene-butadiene rubber

A novel solid-phase method has been proposed to prepare a nanosilica-supported antioxidant by the reaction of nanosilica with 2-mercaptobenzimidazole (MB) and silane coupling agent γ-chloropropyltriethoxysilane. Fourier transform-infrared spectroscopy and other characterization methods confirmed that MB was chemically bonded onto the surface of nanosilica. Silica-s-MB was homogeneously dispersed in a styrene-butadiene rubber (SBR) matrix with strong filler-rubber interaction, leading to enhanced mechanical performance of SBR/silica-s-MB composites compared with SBR/m-silica composites. Based on the results of thermo-oxidation testing of SBR/silica-s-MB and SBR/m-silica/MB composites containing equivalent antioxidant component, silica-s-MB showed better antioxidative efficiency than the corresponding low-molecular-weight MB owing to its lower migration and volatility at high temperature.     

Accelerating role of clay in photo-oxidation of polypropylene/clay multifilament yarns

Photo-oxidative degradation of polypropylene/clay multifilament yarns containing different amounts of clay was investigated. These samples and pure polypropylene(PP) multifilametns were exposed to long wavelength radiations(λ 300 nm) under atmospheric condition of constant temperature and relative humidity. The photo-oxidative stability was studied using FTIR spectroscopy, tensile testing and microscopy. The results indicate that the addition of clay particles decreases the stability of PP/clay composites to photo-oxidative degradation according to comparison with pure PP. From FTIR study and tensile properties, it was also found that the multifilaments with higher clay loading reveals a faster loss of mechanical properties, higher photo-oxidative product formation and more reduction in the induction time of photooxidation. Moreover, the crack formation on surface of irradiated filaments corresponds well to the conclusions in tensile properties and FTIR characterization.     

Fabrication of microporous membranes from melt extruded polypropylene precursor films via stretching: Effect of annealing

In this work, the effects of annealing conditions on the microstructure of polypropylene(PP) precursor films and further on the porous structure and permeability of stretched membranes were investigated. Combinations of WAXD, FTIR, DSC and DMA results clearly showed the crystalline orientation and crystallinity of the precursor film increased with annealing temperature, while the molecular chain entanglements in the amorphous phase decreased. Changes in the deformation behavior suggested more lamellar separation occurred for the films annealed at higher temperatures. Surface morphologies of the membranes examined by SEM revealed more pore number and uniform porous structure as the annealing temperature increased. In accordance with the SEM results, the permeability of the membranes increased with annealing temperature. On the other hand, it was found that 10 min was almost enough for the annealing process to obtain the microporous membranes with an optimal permeability.     

Mechanical characterization of 3D angle-interlock Kevlar/basalt reinforced polypropylene composites

The present work reported the mechanical characterization of novel polypropylene (PP) composites reinforced with three-dimensional angle-interlock (3D-A) Kevlar/basalt fabrics. Two homogeneous fabrics with Kevlar (K3D) and basalt yarns (B3D), and a hybrid fabric (H3D) with a combination of both Kevlar and basalt yarns were produced. Three types of two layer 3D-A composites were manufactured using vacuum-assisted compression molding method. Static tensile and in-plane compression tests were carried out on the manufactured composites. The mechanical behavior of the three 3D-A composites was compared in terms of stress-strain response, elastic modulus, strength and failure strain. Influence of hybridization on the mechanical behavior of the 3D-A composites was also studied. Significant improvement in the tensile behavior of 3D-A homogeneous composites was observed due to hybridization. Meanwhile, there was no considerable improvement in in-plane compression behavior. The damage patterns for in-plane compression loading were examined through scanning electron microscopy (SEM) to explore the possible damage patterns such as matrix cracking, fiber failure, delamination and deformation. Numerical simulations were carried out using ABAQUS/Standard, by implementing a user-defined material subroutine (VUMAT) based on the Chang-Chang linear orthotropic damage model. Good agreement between experimental and numerical simulations was achieved in terms of damage patterns.