Molecular Weight Polypropylene Research Articles

Influence of MIL-53 on the catalytic performance of metallocene in propylene polymerization

In this study, we investigate the application of metal-organic frameworks (MOFs) as a support for metallocene catalysts in the polymerization of propylene. MOFs such as MIL-53 and other conventional supports, SBA-15 and SiO2, were employed to immobilize the Me2Si(2-Me-4-PhInd)2ZrCl2 catalyst activated with methylaluminoxane (MAO). The effects of the physicochemical properties of these supports on catalytic performance and polymer properties were investigated. MIL-53, characterized by its channel structure, facilitated higher molecular weight polypropylene production and exhibited double the catalytic activity of SBA-15 and SiO2 supports. The MIL-53/MAO/Me2Si(2-Me-4-PhInd)2ZrCl2 catalyst also demonstrated higher comonomer incorporation and lower polymer melting points. The higher activity, elevated molecular weight, and increased reactivity towards 1-hexene of the MIL-53/MAO/Me2Si(2-Me-4-PhInd)2ZrCl2 catalyst are attributed to the electronic and steric effects of MIL-53. This study underscores the significant role of MOF structure in influencing polymerization behavior and highlights the potential of MOF-supported catalysts for tailored polymer properties.

Dynamic behavior of melt electrospinning of blended polypropylene

Melt electrospinning is a promising process for fiber production without the need for solvents and with potential applications in various fields. In this study, we investigated the dynamic behavior of melt electrospinning under different blending ratios and process conditions. We used high melt flow index polypropylene and low molecular weight polypropylene, which were blended to lower the melt viscosity, and fibers were successfully manufactured through the melt electrospinning process. The effects of blending ratio and applied voltage on jet and drop formation, as well as fiber morphology, were examined. The results showed that blending low-molecular-weight polypropylene significantly influenced the jet and drop areas, leading to fluctuations in jet morphology. The size of the applied high voltage also had a high effect on the fiber diameter. Additionally, the viscosity reduction achieved through blending allowed for continuous jet formation and improved fiber production. These results provide valuable insights into controlling the process parameters and blending ratios in melt electrospinning, enabling the establishment of stable electrospinning conditions and precise control of fiber diameter.

Absorption of Polypropylene in Dipalmitoylphosphatidylcholine Membranes: The Role of Molecular Weight and Initial Configuration of Polymer Chains.

We study by molecular dynamics simulations the absorption of polypropylene (PP) chains within a dipalmitoylphosphatidylcholine (DPPC) lipid membrane in aqueous solvent. DPPC represents the most abundant phospholipid in biological membranes, while PP is one of the most common synthetic polymers diffused in the anthropic environment. By following in detail the absorption process, and the corresponding structural modification undergone by the membrane, we show how the initial configuration and the PP molecular weight determine the overall behavior of the system. Specifically, if PP chains initially lie on the DPPC surface, they are fully absorbed; likewise, polymers initially included within the membrane cannot escape from. On the other hand, if polymers are placed sufficiently apart from the membrane, they have time to join together and coalesce into a few nanoparticles. At contact, such nanoparticles may completely dissolve (for low molecular weight) and then be absorbed. For high molecular weight, not all of them dissolve, and therefore the system attains a condition in which some of the chains are absorbed, while others form a residual nanoparticle staying outside (but in contact with) the membrane. Such a state─albeit energetically unfavorable with respect to a condition in which all PP chains are absorbed─remains stable, at the least over a substantial simulation time, extending in our study up to 1.6 μs. The tendency for polymers to spontaneously form aggregates, which then prefer to stay in contact with the membrane, is further corroborated by calculation of the DPPC-nanoparticle potential of mean force.

Impact of polymer molecular weight and dispersity on the coalescence of polypropylene powders suitable for laser powder bed fusion

Understanding and controlling the fundamental processes governing the coalescence of polymers is vital to enable the design of polymeric materials for improved mechanical performance and quality of manufactured structures, including those fabricated via additive manufacturing techniques. Our group has utilized thermally induced phase separation (TIPS) to produce spherical and size controlled polypropylene (PP) powders from 12,000 (12k), 250,000 (250k), and 340,000 (340k) molecular weight (Mw) PP, including 50-50 wt% blends of 12k/250k,12k/340k, and 250k/340k, and a 33-33-33 wt% blend of 12k/250k/340k to investigate the impact of polymer Mw, and thus zero-shear viscosity, on particle coalescence and its implication in laser powder bed fusion. The particles exhibit similar size distributions with an average particle size, Dx(50), in the range of 58 μm–86 μm. The coalescence behavior of the powders, evaluated via hot-stage microscopy, show that adding 12k PP in the blend significantly alters the coalescence dynamics of the 250k and 340k PP, dramatically increasing their coalescence rate. The substantial drop in zero-shear viscosity with addition of 12k PP provides the driving force for the pronounced enhancement in coalescence. Strong agreement between experimental results and the Hopper model of coalescence is observed only if corrected for extensional flow, exemplifying the importance of extensional flow on the coalescence process. The results also indicate that the 12k PP in the blend does not surface segregate in the TIPS process, but is homogeneously distributed in the blend. More broadly, these results provide molecular-level insight into how control of powder molecular weight characteristics and viscosity can offer pathways to optimize the consolidation of particles in manufacturing processes, including laser powder bed fusion.

Facilely prepare ultra-high molecular weight polypropylene loose nanofiltration membrane for efficient dye/salt separation

The simple strategies and processes for preparing nanofiltration (NF) membranes with well-pore channels and high separation efficiency have received growing attention in academia. Herein, ultra-high molecular weight polypropylene (UHMWPP) has been successfully fabricated into high-performance loose NF membranes through thermally induced phase separation (TIPS). The results showed that the as-prepared UHMWPP loose NF membrane has a good water permeance (17.7 L m−2 h−1 bar−1), a high RB rejection (99 %), and a low inorganic salt retention rate (NaCl: 1.9 %), which makes the loose NF membrane a potential choice for dye/salt separation. In addition, the membrane also has good antifouling properties, acid and alkaline resistance, and long-term stability. Thus, this work offers a viable and pragmatic technical approach for addressing high-salt printing and dyeing wastewater, with broad prospects for application and practical value.

Kinetics in high-temperature free-radical reactive processing: Grafting maleic anhydride onto polypropylene in the presence of nanoclay-supported peroxide

The kinetics of grafting and chain scission reactions during maleic anhydride (MA) grafting onto polypropylene (PP) using nanoclay-supported peroxide (o-MMT/DCP) in the molten state were evaluated through the development of a new methodology. A combination of characterization techniques and mathematical data manipulation was employed for this assessment. To inhibit radical propagation and recombination, tetramethylpiperidine-1-oxyl (TEMPO) was used as a free radical scavenger. Rheological stability tests demonstrated that TEMPO was more effective as a reaction inhibitor. The kinetics dataindicated that the use of o-MMT/DCP resulted in products with higher MA grafted levels and molecular weight (MW) compared to grafting performed in the absence of o-MMT. Additionally, some changes in molecular architecture were observed. The chain scission distribution function (CSDF) revealed that during the MA grafting process, the molecular weight of PP was reduced through chain scission, with a preference for longer chains. Furthermore, the presence of o-MMT was found to restrain the level of PP chain scission, likely due to recombination on the clay surface.

Basalt/polypropylene composites: The effects of mechanical reprocessing on their morphological, thermal, rheological and mechanical behavior

Considering the increasing spread of basalt fibers on the market as bio-based alternative to glass and the massive use of polypropylene (PP) in the automotive sector, the end-of-life of PP/basalt composites through mechanical reprocessing was addressed. Their thermal, rheological and mechanical properties were investigated up to seven reprocessing cycles and the main relationship between their changes and composites fibers length reduction was disclosed. The composites displayed a parabolic increase in their melt volume rate for increasing reprocessing cycles and were characterized by an improved flowability compared to the neat matrix at the fifth cycle, i.e., 89.3 against 74.8 cm3/10min, due to the intimate contact between the fibers and the matrix which causes a stronger degradation in PP molecular weight. Concerning the mechanical response, the logarithmic decrease in stiffness and strength was not directly proportional to fibers length reduction due to a progressive better orientation of the fibers along the injection direction. Finally, the comparison of the mechanical results obtained with the data available for PP composites reinforced with vegetable fibers allowed to conclude that PP/basalt composites are competitive with this type of composites up to the fifth cycle, displaying a tensile modulus of 3.5 GPa and tensile strength of 38 MPa.

A hybrid steric ligand modification strategy promotes propylene (co)polymerization

Recently, a Hybrid Steric Ligand Modification (HSLM) strategy has been shown to significantly increase the polymerization activity and the branching degree of the resulting (co)polymers in the ethylene (co)polymerization via α-diimine catalysts. In this study, the HSLM strategy was employed for propylene (co)polymerization using a group of α-diimine Pd(II) catalysts with bulky hybrid ligands. The HSLM catalysts (Pd1-4) produced polypropylene with high molecular weights (45.4–156.9 kg/mol) and resulted in significantly high levels of activity (105 g mol−1 h−1). Additionally, nearly half of the propylene underwent chain straightening (1,3-enchainment = 43–46 %). Our findings suggest that Pd1-4 catalysts are more effective than the symmetrical catalysts Pd5-6 in producing high molecular weight polypropylene with high activity. Among all the catalysts tested, Pd4 with 4-tert-butylphenyl displayed the highest polymerization activity and molecular weight, although with lowest branching densities. It is suggested that the HSLM may provide a more open spatial configuration around the metal center, which facilitates the coordination and insertion of propylene molecules as well as chain walking. The hybrid Pd(II) catalysts showed moderate activity during the copolymerization of propylene with MA. The copolymers produced had low molecular weights (3.1–11.2 kg/mol), high branching densities (120–211/1000C), and high incorporation ratios (8.82–18.08 mol%). The copolymerization activity was highest with 4-tert-butylphenyl Pd4. The resulting P-MA copolymers had the highest molecular weight, the largest branching degree, and the lowest incorporation ratios.

Molecular-Weight-Dependent Degradation of Plastics: Deciphering Host-Microbiome Synergy Biodegradation of High-Purity Polypropylene Microplastics by Mealworms.

The biodegradation of polypropylene (PP), a highly persistent nonhydrolyzable polymer, by Tenebrio molitor has been confirmed using commercial PP microplastics (MPs) (Mn 26.59 and Mw 187.12 kDa). This confirmation was based on the reduction of the PP mass, change in molecular weight (MW), and a positive Δδ13C in the residual PP. A MW-dependent biodegradation mechanism was investigated using five high-purity PP MPs, classified into low (0.83 and 6.20 kDa), medium (50.40 and 108.0 kDa), and high (575.0 kDa) MW categories to access the impact of MW on the depolymerization pattern and associated gene expression of gut bacteria and the larval host. The larvae can depolymerize/biodegrade PP polymers with high MW although the consumption rate and weight losses increased, and survival rates declined with increasing PP MW. This pattern is similar to observations with polystyrene (PS) and polyethylene (PE), i.e., both Mn and Mw decreased after being fed low MW PP, while Mn and/or Mw increased after high MW PP was fed. The gut microbiota exhibited specific bacteria associations, such as Kluyvera sp. and Pediococcus sp. for high MW PP degradation, Acinetobacter sp. for medium MW PP, and Bacillus sp. alongside three other bacteria for low MW PP metabolism. In the host transcriptome, digestive enzymes and plastic degradation-related bacterial enzymes were up-regulated after feeding on PP depending on different MWs. The T. molitor host exhibited both defensive function and degradation capability during the biodegradation of plastics, with high MW PP showing a relatively negative impact on the larvae.

Towards effective recycling routes for polypropylene: Influence of a repair additive on flow characteristics and processability

Plastic recycling is a key aspect to achieve effective polymer circularity, especially for polyolefins for which usually the mechanical recycling is considered a downcycling process. This downcycling phenomenon arises from the progressive deterioration of the polymer microstructure during reprocessing, resulting in a gradual loss of processability and properties, ultimately compromising the possibility of using recycled polyolefins for applications with high engineering requirements.In this work, the effects of the thermomechanical degradation on the microstructure of polypropylene (PP) were assessed by subjecting the polymer to multiple extrusion cycles. The objective is investigating the evolution of the molecular weight and of the macromolecular architecture of PP typically occurring in a mechanical recycling process.Furthermore, a commercially available additive capable of restoring the PP molecular weight was introduced, with the purpose of proposing an effective upcycling strategy for achieving recycled PP with enhanced processability. In particular, the effects of the additive were evaluated following two different strategies that simulate pre-consumer or post-consumer mechanical recycling.The obtained results indicated that the introduction of the additive can effectively prevent the decrease of the molecular weight of reprocessed PP, also inducing some melt structuring phenomena associable with the introduction of some long chain branching and/or crosslinking. Finally, it was demonstrated that different macromolecular architectures for recycled PP can be achieved depending on the residence time during the processing in presence of the additive, opening new perspectives towards the possibility of obtaining recycled PP with modulable flow characteristics and, hence, processability.

On the Mechanical, Thermal, and Rheological Properties of Polyethylene/Ultra-High Molecular Weight Polypropylene Blends.

The novel ultra-high molecular weight polypropylene (UHMWPP) as a dispersed component was melt blended with conventional high-density polyethylene (PE) and maleic anhydride grafted-polyethylene (mPE) in different proportions through a kneader. Ultra-high molecular weight polypropylene is a high-performance polymer material that has excellent mechanical properties and toughness compared to other polymers. Mechanical, thermal, and rheological properties were presented for various UHMWPP loadings, and correlations between mechanical and rheological properties were examined. Optimal comprehensive mechanical properties are achieved when the UHMWPP content reaches approximately 50 wt%, although the elongation properties do not match those of pure PE or mPE. However, it is worth noting that the elongation properties of these blends did not match those of PE or mPE. Particularly, for the PE/UHMWPP blends, a significant drop in tensile strength was observed as the UHMWPP content decreased (from 30.24 MPa for P50U50 to 13.12 MPa for P90U10). In contrast, the mPE/UHMWPP blends demonstrated only minimal changes in tensile strength (ranging from 29 MPa for mP50U50 to 24.64 MPa for mP90U10) as UHMWPP content varied. The storage modulus of the PE/UHMWPP blends increased drastically with the UHMWPP content due to the UHMWPP chain entanglements and rigidity. Additionally, we noted a substantial reduction in the melt index of the blend system when the UHMWPP content exceeded 10% by weight.

Evaluating the molecular weight distribution of ultrahigh molecular weight polypropylene through rheology

This work investigates the possibility of obtaining the molecular weight distribution (MWD) of linear ultrahigh molecular weight (UHMW) polypropylene (PP) through rheology. To this end, the linear viscoelastic response of a set of UHMWPP samples is measured over the largest possible frequency range. The terminal relaxation is achieved by running creep experiments and converting the compliance in dynamic moduli. A time–temperature concentration principle, recently validated for UHMW polyethylene, is also applied to obtain the terminal relaxation of the sample with the largest molecular weight. The linear rheological response is correlated with gel permeation chromatography (GPC) results by means of the mixing rule based on the relaxation modulus. The implementation of such a rule requires the knowledge of some material parameters governing the stress relaxation of the polymer. Since they are unknown in literature for PP, they are estimated from the comparison between the viscoelastic spectra and the GPC distributions of three lab-made UHMWPPs with narrow polydispersity. Such parameters are then used as a basis to predict the MWDs of two UHMWPP samples with large polydispersity. The variability of the parameters upon molecular weight and polydispersity is assessed by applying the mixing rule to two different PP samples with lower molecular weights, one with narrow polydyspersity and another one with broad polydispersity. As the GPC curves of the samples are available, first the direct problem of estimating the rheological response from MWD and then the inverse problem of obtaining the MWD from the rheological data are solved. An overall satisfactory agreement is found between the calculated and measured MWD for the two samples, with both the direct and inverse approach.

Fabrication of novel biocomposite made of chemically treated sludge fibers and various molecular weight polypropylene

The effect of the chemical treatment of paper mill sludge fibers and polypropylene molecular weight were studied relative to the physical, mechanical, and morphological properties of a novel cellulosic biocomposite. Paper mill sludge fibers were treated with acetic anhydride, and succinic anhydride was mixed with maleic anhydride polypropylene (MAPP) and coupling agent (0 and 3%). The ratio of fibers and polymer materials was considered 30 to 70, which was manufactured by the hot-pressing method at 180 °C. Water absorption, volume swelling, and contact angle were examined on each specimen according to ASTM standards, while Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) explored the efficiency of chemical modification of fibers and the morphology of biocomposites, respectively. The results showed that chemical treatment of fibers reduced the water absorption and volumetric swelling. Both tensile and flexural strength were increased with chemical treatment using the coupling agent. Comparison of fibers treated with succinic acid and acetic acid showed that the succinic acid enhanced the mechanical properties better than the acetic acid treatment. Finally, FTIR analysis showed that the hydroxyl groups decreased, and SEM images indicated the interface between fibers and polypropylene improved via chemical treatment of sludge fibers.

Properties of blends of ultra-high molecular weight polypropylene with various low molecular weight polypropylenes

To enhance the ease of processability of the ultra-high molecular weight polypropylene (UHMWPP), the various low molecular weight polypropylenes (LMWPPs) blended with the UHMWPP via a facile melt blending process. The effect of the LMWPPs component on the UHMWPP component on its rheological and mechanical properties was characterized using various measurement techniques. The processability of the UHMWPP was improved drastically with the introduction of LMWPP components as the melt index of the blend increased. As the LMWPP content increases, the mechanical properties of the blends tend to increase or decrease, depending on the type of LMWPP.

Delamination behaviour and surface morphology of wholly thermoplastic composites using different ultra-high molecular weight thermoplastic fabrics with pristine and toughened Elium resin under Mode I loading

Current research investigates the manufacturing and bonding characteristics of wholly thermoplastic composites with thermoplastic fibres and acrylic Elium® resin and toughened Elium®IM with 10% weight acrylonitrile butadiene styrene (ABS) particles under Mode I loading. Ultra-high molecular weight polypropylene (UHMWPP)/Elium® IM and UHMWPP/Elium® composites have shown 43.9% and 24.5% higher critical energy release rate compared to epoxy composite systems, while a similar trend was observed in the case with composites with polyester as the reinforcement system. For ultra-high molecular weight polyethylene (UHMWPE)/Elium®, the increase was only 13.7% but with the use of toughened thermoplastic variant, the increase was found to be 36.8% higher. Detailed microscopic examination reported fibre bridging, pull-out, strong fibre–matrix adhesion, riverlines, and matrix deformation owing to the ductile characteristic of Elium® resin. ABS-modified Elium®IM composites have shown rough matrix fracture surface and there was internal cavitation of ABS particles followed by crack growth and local shear band formation.

Understanding the impact properties and damage phenomenon of ultra-lightweight all-thermoplastic composite structures

The current research presents the details of the impact properties of novel all-thermoplastic composite structures with different thermoplastic fabrics like ultra‐high molecular weight polyethylene (PE), ultra‐high molecular weight polypropylene (PP), and Polyester (PES) with room temperature curable acrylic Elium® (EL) thermoplastic resin. The low-velocity impact performance is studied at five energy levels (10J-50J), and the performance is compared to baseline epoxy (EP) composites, and their failure mechanisms are deduced through optical and SEM examination. PP/ELC, PE/ELC and PES/ELC all-thermoplastic composites have shown up to 34.68%, 24.46%, 15.35 % higher load carrying capability and 27%, 11.21%, 8.43% lower absorbed energy compared to PP/EPC, PE/EPC, and PES/EPC composites respectively due to the lesser damage and high toughness of the matrix. The major damage energy was found to be 10.55% higher due to the more elastic and plastic deformation mechanisms before the onset of the damage. PP/ELC, PE/ELC, and PES/ELC have shown 32%, 66.7% and 51% improvement in structural integrity as opposed to epoxy counterparts. ELC composites have shown matrix cracks, and strong fibre matrix adhesion with thermoplastic fibres properly embedded in the acrylic resin, while clean fibre pull-out and bare fibres were observed for EPC composites.

On the Mode I and Mode II Delamination Characteristics and Surface Morphological Aspects of Composites with Carbon-Thermoplastic Hybrid Fabrics and Innovative Liquid Thermoplastic Resin.

In the current research, the delamination behavior under Mode I and Mode II loading for the hybrid carbon-thermoplastic fabrics in conjunction with novel liquid thermoplastic acrylic Elium® resin processable at ambient conditions was studied. The experimentation by incorporating doublers methodology, studying the performance under Mode I and Mode II loading, and understanding failure mechanisms using surface morphological fractography is deliberated. Hybrid Carbon-Ultra-high molecular weight polyethylene (UHMWPP)/Elium® composite has shown a 22.81% higher GIC and a 22.2% higher GIIC than Carbon-UHMWPP/Epoxy composite. On the contrary, the Carbon_Ultra-high molecular weight polypropylene (UHMWPE)/Elium® has shown an 11.11% higher Mode I critical energy release rate (GIC) and a 7.58% higher Mode II critical energy release rate (GIIC) than Carbon_UHMWPE/Epoxy composite. Hybrid fiber reinforced thermoplastic composites have shown severe plastic deformation of the matrix, rough fracture surface, and micro-cracks on the de-bonding surface, extensive fiber bridging, and crack branching which contributed to the improvement in the delamination behavior. Hybrid fiber architecture is also found to be detrimental by inducing crack arresting mechanisms including the tortuous crack path and the resin-rich pockets path due to the mismatch of the size of the fiber yarns.

Rheological, Mechanical, and Thermal Properties of Ultrahigh Molecular Weight Polypropylene/Low Molecular Weight Polypropylene Blends

Ultra-high molecular weight polypropylene (UHMWPP), with a molecular weight of more than 106 g/mol, is expected to have superior properties, such as high mechanical strength, high thermal properties, high chemical resistance and outstanding tribological properties. However, UHMWPP has a very poor processability due to its high melt viscosity. Therefore, we aimed to improve processability of UHMWPP by blending it with a low molecular weight polypropylene (LMWPP). We attempted to improve the interfacial miscibility and intermolecular entanglement of the UHMWPP/LMWPP system by using a kneader machine. The addition of LMWPP tended to change the mechanical, thermal, and rheological properties of the blend system.

On the Mode II fracture toughness, failure, and toughening mechanisms of wholly thermoplastic composites with ultra-lightweight thermoplastic fabrics and innovative Elium® resin

Current work presents the first investigation on the Mode II fracture toughness of room temperature curable acrylic Elium® resin and toughened Elium®IM with 10% weight acrylonitrile butadiene styrene (ABS) particle with different thermoplastic fabrics like Ultra-high molecular weight polyethylene (UHMWPE), Ultra-high molecular weight polypropylene (UHMWPP), and polyester. The testing methodology using doublers, performance under Mode II loading and understanding the failure and toughening mechanisms is deliberated. GIIC of UHMWPP/Elium®IM composite was found to be 33.3% higher than that of UHMWPP/Epoxy composite. Polyester/Elium® composites have 27.02% higher GIIC than Polyester/Epoxy composites while Polyester/Elium®IM composites exhibited the highest GIIC which was 17.76% higher than Polyester/Elium® composites. Fractography of toughened Elium®IM composites displayed significant resistance to crack propagation that generated a rough and shear deformed curved layer type of de-bonding surface due to the extra toughening provided by particles which generated the crack deflection and void resulting from cavitation of ABS particles.

Investigation of Curing Mechanism and Mechanical Properties of Polypropylene/Aliphatic Epoxy Composites

Temperature-sensitive cure kinetics based on bisphenol A oligomeric diglycidyl ether and branching diphenylmethane di-isocyanate, polymer aliphatic or lower molecular weight aromatic amines, and polypropylene and epoxy composites were examined. Polypropylene networks are formed initially, followed by amine hardeners interfering with epoxy oxirane rings to frame linear oligomers. Finally, the system is formed by a reaction between amines obtained in the second phase and epoxy oxirane rings during the curing step. This three-stage treatment was illustrated. The activation energy was calculated using the Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose isoconversational approaches to cure degree. The Ea-to-αcorrelation was determined using these approaches, revealing that the research curing systems exhibited autocatalytic effects. Among the materials studied, compounds with low molecular weight aromatic amines had the strongest and longest-lasting tensile characteristics. There are numerous advantages to slow curing and discrete stages of composite creation, including better mechanical properties.