Propylene Copolymer Research Articles

Transformative and sustainable approach to waste plastic mixture valorization

The development of innovative methods for waste plastic valorization can benefit the environment and economy. In this study, the full spectrum of products (gas, oil, and solid products) resulting from the pyrolysis–reforming of a plastic mixture functioned as precursors of value-added products: 1) ethylene–propylene copolymers, 2) polyacrylonitrile (PAN)-based carbon nanofibers (CNFs), and 3) carbon quantum dots (CQDs). The CNFs were subsequently applied as supercapacitor electrodes, whereasthe CQDs acted as co-sensitizers for the primary sensitizer, N3, in dye-sensitized solar cells (DSSCs). Adding oil to PAN increased the specific capacitance of the CNFs by 46.12% to 226.64F/g, compared with that of pure PAN CNFs. With the aid of CQDs, the short-circuit current density and photo-conversion efficiency of DSSCs increased by 25.89% and 17.08%, respectively. Mechanisms associated with the integrated valorization pathway were proposed.

Investigation on the oil permeation–adsorption–diffusion combined action mechanism of the adsorbed layer for flexible oil storage in waters

A novel method entitled flexible oil storage in waters is proposed, aiming to address the limitations of current oil storage systems and enhance the country's oil storage capacity. However, oil contamination severely restricts its applicability. To ensure the environmental sustainability of the method, the adsorbed layer is added outside the oil bladder, and the study investigates the material and the action mechanism of the adsorbed layer for flexible oil storage in waters. The results show that, with long breakthrough time and low oil concentration as criteria, the reed straw biochar is more suitable as the adsorbed layer filling material compared to the coconut shell and the apricot shell biochar and the fluorinated ethylene propylene copolymer is more suitable as the adsorbed layer membrane material compared to polyvinyl chloride. The adsorbed layer action mechanism involves multiple interactions, including permeation, adsorption, accumulation, and diffusion. They are coupled and together influence the adsorption effect. The empirical formula for the adsorbed layer's lifespan is derived, which helps in designing the adsorbed layer to satisfy specific lifespan requirements. This study provides theoretical and engineering guidance for the application of flexible oil storage in waters, contributing to the development of oil storage techniques.

Revealing the Molecular Interaction between CTL Base Oil and Additives and Its Application in the Development of Gasoline Engine Oil

In order to improve fuel economy to meet the standard for passenger car oil, a new formulation with good viscosity–temperature performance for gasoline engine oil is required. In this study, coal-to-liquid (CTL) base oil, with a high viscosity index and good low-temperature performance, was selected as the base oil to develop the gasoline engine oil. A systematic study on the molecular interaction between the CTL base oil and the viscosity index improver (VII), including three kinds of hydrogenated styrene diene copolymers (HSD-type) and four kinds of ethylene propylene copolymers (OCP-type), was conducted. It was found that in general, in CTL base oil, the HSD-type VII exhibited a much higher viscosity index, a significantly lower shear stability index, a higher thickening ability, and a lower cold-cranking simulator (CCS) viscosity than that of OCP-type VII. Moreover, when comparing CTL base oil with mineral oil 150N, the combination of CTL base oil and the VII displayed a lower CCS viscosity than that of mineral oil, suggesting it had better low-temperature performance and was able to quickly form a protective oil film on the surface, which was beneficial for the cold start. The functional group distribution state of the VII in base oil was analyzed using synchrotron radiation micro-infrared microscope (SR Micro-IR) technology, which revealed that HSD-1 had a better molecular interaction with CTL6 than 150N because of the better uniformity of the C=C group distribution. Based on this, a SP 0W-20 gasoline engine oil was developed by the combination of CTL base oil and the HSD-1 viscosity index improver, together with an additive package, a polymethacrylate pour point depressant, and a non-silicone defoamer, which showed excellent low-temperature performance, thermal oxidation stability, and detergency performance compared to the reference oil.

Research on the Influence of Core Sensing Components on the Performance of Galvanic Dissolved Oxygen Sensors.

The galvanic dissolved oxygen sensor finds widespread applications in multiple critical fields due to its high precision and excellent stability. As its core sensing components, the oxygen-permeable membrane, electrode, and electrolyte significantly impact the sensor's performance. To systematically investigate the comprehensive effects of these core sensing components on the performance of galvanic dissolved oxygen sensors, this study selected six types of oxygen-permeable membranes made from two materials (Perfluoroalkoxy Polymer (PFA) and Fluorinated Ethylene Propylene Copolymer (FEP)) with three thicknesses (0.015 mm, 0.03 mm, and 0.05 mm). Additionally, five concentrations of KCl electrolyte were configured, and four different proportions of lead-tin alloy electrodes were chosen. Single-factor and crossover experiments were conducted using the OxyGuard dissolved oxygen sensor as the experimental platform. The experimental results indicate that under the same membrane thickness conditions, PFA membranes provide a higher output voltage compared to FEP membranes. Moreover, the oxygen permeability of FEP membranes is more significantly affected by temperature. Furthermore, the oxygen permeability of the membrane is inversely proportional to its thickness; the thinner the membrane, the better the oxygen permeability, resulting in a corresponding increase in sensor output voltage. When the membrane thickness is reduced from 0.05 mm to 0.015 mm, the sensor output voltage for PFA and FEP membranes increases by 86% and 74.91%, respectively. However, this study also observed that excessively thin membranes might compromise measurement accuracy. In a saturated, dissolved oxygen environment, the sensor output voltage corresponding to the six oxygen-permeable membranes used in the experiment exhibits a highly linear inverse relationship with temperature (correlation coefficient ≥ 98%). Meanwhile, the lead-tin ratio of the electrode and electrolyte concentration have a relatively minor impact on the sensor output voltage, demonstrating good stability at different temperatures (coefficient of variation ≤ 0.78%). In terms of response time, it is directly proportional to the thickness of the oxygen-permeable membrane, especially for PFA membranes. When the thickness increases from 0.015 mm to 0.05 mm, the response time extends by up to 2033.33%. In contrast, the electrode material and electrolyte concentration have a less significant effect on response time. To further validate the practical value of the experimental results, the best-performing combination of core sensing components from the experiments was selected to construct a new dissolved oxygen sensor. A performance comparison test was conducted between this new sensor and the OxyGuard dissolved oxygen sensor. The results showed that both sensors had the same response time (49 s). However, in an anaerobic environment, the OxyGuard sensor demonstrated slightly higher accuracy by 2.44%. This study not only provides a deep analysis of the combined effects of oxygen-permeable membranes, electrodes, and electrolytes on the performance of galvanic dissolved oxygen sensors but also offers scientific evidence and practical guidance for optimizing sensor design.

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.

Microstructure, Viscoelasticity, and Extensional Rheology of Ethylene–Propylene Copolymer Vitrimers

Microstructure, Viscoelasticity, and Extensional Rheology of Ethylene–Propylene Copolymer Vitrimers

Synthesis of Polar-functionalized Isotactic Polypropylenes Using Commercial Heterogeneous Ziegler-Natta Catalyst.

The efficient synthesis of polar-functionalized polypropylenes with high molecular weight and high stereoregularity represents a challenging task. This challenge becomes even more daunting when pursuing an industrially preferred heterogeneous process. This study demonstrated the realization of these goals through the use of commercial heterogeneous Ziegler-Natta catalysts in the copolymerization of propylene with ionic cluster polar monomers. The results revealed high copolymerization activity (∼1.1 × 107 g mol-1 h-1), moderate polar monomer incorporation ratios (∼4.9 mol %), high copolymer molecular weight (Mw > 105 g mol-1), high stereoregularity ([mmmm] ∼ 96%), and high melting temperature range (150-162 °C). The utilization of ionic cluster polar monomers improved the thermal stability as well as stereoselectivity of the catalyst. Moreover, the Ziegler-Natta catalyst can homopolymerize ionic cluster polar monomers with high activities (>104 g mol-1 h-1). The resulting polar-functionalized isotactic polypropylenes (iPP) exhibited superior tensile strength, impact strength, creep resistance, transparency, and crystallinity compared with nonpolar iPP. This enhancement was attributable to the dual roles of the ionic cluster polar monomer unit, serving as both a transparent nucleating agent and a dynamic cross-linking functionality. Furthermore, the polar-functionalized iPP exhibited improved compatibility with polar materials, offering benefits for applications in composites, recycling of mixed plastic wastes, 3D printing, and other fields. This study offered a comprehensive solution for the future industrial production of polar-functionalized iPP via copolymerization, bridging the gap between an efficient and practical copolymerization process from a synthetic chemistry perspective and enhanced material properties from an application perspective.

Investigation of Crystallization, Morphology, and Mechanical Properties of Polypropylene/Polypropylene-Polyethylene Block Copolymer Blends.

Polyethylene (PE)-based elastomers are the ideal choice for enhancing the compatibility of polypropylene/polyethylene (PP/PE) blends and improving the mechanical properties of PP-based materials. However, the issue of blend systems lies in the interplay between the crystallization processes. Therefore, we investigated the crystallization behavior during the cooling process of a new generation of PP/PE block copolymers (PP-b-PE) and random polypropylene (PPR, a copolymer of propylene and a small amount of ethylene or an alpha-olefin) blends using in-situ X-ray diffraction/scattering and differential scanning calorimetry (DSC) techniques. We also conducted mechanical performance tests on PPR/PP-b-PE blends at room temperature and low temperature (-5 °C). The results indicate that during the cooling process, the PP phase of PP-b-PE will follow the PPR to crystallize in advance and form a eutectic mixture, thereby enhancing the compatibility of PP/PE. Moreover, the PPR/PP-b-PE blend will form stable β-(300) crystals with excellent mechanical properties. Due to the improved compatibility of PP/PE with PP-b-PE, PE crystals are dispersed within PP crystals, providing bonding that improves the toughness of PPR under the low stiffness failure conditions of PPR/PP-b-PE blends, thereby enhancing their impact performance at low and room temperatures. This research has great significance for both recycling waste plastics and enhancing the low-temperature toughness of PPR.

On‐Line Monitoring Device for Gas Phase Composition Based on Machine Learning Models and Its Application in the Gas Phase Copolymerization of Olefins

AbstractThis study addresses the challenges of time‐delay and low accuracy in online gas‐phase composition monitoring during olefin copolymerization processes. Three flowmeters based on different mechanisms are installed in series to measure the real‐time exhaust gas flow rate from the reactor. For the same gas flow, the three flowmeters display different readings, which vary with the properties and composition of the gas mixture. Consequently, the composition of the mixed gas can be determined by analyzing the reading of the three flowmeters. Fitting equations and three machine learning models, namely decision trees, random forests, and extreme gradient boosting, are employed to calculate the gas composition. The results from cold‐model experimental data demonstrate that the XGBoost model outperforms others in terms of accuracy and generalization capabilities. For the concentration of ethylene, propylene, and hydrogen, the determination coefficients (R2) were 0.9852, 0.9882, and 0.9518, respectively, with corresponding normalized root mean square error (NRMSE) values of 0.0352, 0.0312, and 0.0706. The effectiveness of the online monitoring device is further validated through gas phase copolymerization experiments involving ethylene and propylene. The yield and composition of the ethylene and propylene copolymers are successfully predicted using the online measurement data.

Enhancing Metallocene Catalyst Activity: Utilizing Layered Double Hydroxide for Ethylene–Propylene Copolymerization

AbstractThis study reports the heterogenization of metallocene catalysts on sodium dodecyl sulfate (DDS)‐modified layered double hydroxides (LDHs) for efficient ethylene–propylene (EP) slurry‐phase copolymerization. The LDH support offers considerable compositional tunability. NiFe LDHs with different anions () and metallic compositions are applied as support for the metallocene catalysts; these significantly influence the catalytic properties of the heterogenized catalyst system. The supported‐catalyst intercalating DDS− anion in the galleries of NiFe and ZnAl LDHs demonstrates a high catalytic activity. They produce EP copolymers with high molecular weights (Mw) and wide polydispersity, compared with the homogeneous Zr catalyst. Further, the supported catalyst complex containing anion produces EP with a tenfold high Mw and demonstrate subdued catalytic activity. The higher basicity of the support is associated with the enhanced activity and the wider polydispersity of the EP pertaining to the different interactions of the catalyst molecule with the support. Overall, Ni‐containing LDH favors a higher activity, whereas Fe‐containing LDH favors a higher Mw. Therefore, NiFe‐based LDH results in both higher activity and molecular weight. 13C and 27Al magnetic angle spinning solid‐state nuclear magnetic resonance confirm the formation of the supported catalyst complex.

Ti(IV) Complexes with OSSO-Type Diol Ligands as Catalysts for Synthesis of Ultrahigh-Molecular-Weight Polyethylene and Ethylene–Propylene Copolymers

Ti(IV) Complexes with OSSO-Type Diol Ligands as Catalysts for Synthesis of Ultrahigh-Molecular-Weight Polyethylene and Ethylene–Propylene Copolymers

Stable and long-life Zn anode enabled by an ion-conductive copolymer coating for rechargeable aqueous batteries

The Zn metal anode endows aqueous zinc-ion batteries (ZIBs) with merits in terms of low cost, high safety, and bivalent ions as charge carriers. Yet the current ZIB technology is immature due to some issues arising from the Zn anode, including the dendrite growth, formation of compound byproducts, and hydrogen gas evolution. Here, a nanoporous and ion-conductive polyvinylidene fluoride-hexafluoro propylene copolymer containing zinc trifluoromethanesulfonate (Zn2+-PVDF-HFP coating) is applied onto the Zn foil to improve its anode performance. The Zn anode covered with Zn2+-containing PVDF-HFP coating (Zn@Zn2+-PVDF-HEP) shows good anti-corrosion performance and much longer cycle life, compared to the bare Zn anode. Also, the byproduct growth and hydrogen gas evolution can be efficiently suppressed due to the Zn2+-conductive copolymer coating. For symmetric cells using Zn@Zn2+-PVDF-HFP, a long lifespan of 2200 cycles is achieved when tested at 1 mA cm−2 and 1 mAh cm−2. Even cycled at 10 mA cm−2 and 5 mAh cm−2, this cell can sustain for over 1800 h. The efficacies of Zn2+-PVDF-HFP coating in prolonging cycle life and enhancing areal capacity of the Zn anode are further verified in MnO2- or V2O5-based full cells, for which the mechanisms are discussed in detail.

Airborne hydrophilic microplastics in cloud water at high altitudes and their role in cloud formation

Microplastic pollution is occurring in most ecosystem, yet their presence in high altitude clouds and their influence on cloud formation and climate change are poorly known. Here we analyzed microplastics in cloud water sampled at the summits of Japan mountains at 1300–3776 m altitude by attenuated total reflection imaging and micro-Fourier transform infrared spectroscopy. We observed nine microplastics including polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyamide 6, polycarbonate, ethylene–propylene copolymer or polyethylene–polypropylene alloy, polyurethane, and epoxy resin. Microplastic were fragmented, with mean concentrations ranging from 6.7 to 13.9 pieces per liter, and with Feret diameters ranging from 7.1 to 94.6 μm. Microplastics bearing hydrophilic groups such as carbonyl and/or hydroxyl groups were abundant, suggesting that they might have acted as condensation nuclei of cloud ice and water. Overall, our finding suggest that high-altitude microplastics cloud influence cloud formation and, in turn, might modify the climate.

Palladium-catalyzed copolymerization of ethylene or propylene with norbornene carboxylic acids and their esters

Here, we report copolymerization of ethylene or propylene with norbornenes functionalized with polar groups, using palladium catalysts, Pd/IzQO, Pd/BPMO, or Pd/PS. In this study, the structural analyses for copolymers of ethylene with methyl 5-norbornene-2-carboxylate (E/MeNBE), tert-butyl 5-norbornene-2-carboxylate (E/tBuNBE), or 5-norbornene-2-carboxylic acid (E/NBA) were conducted. Also, this work serves as the first example of coordination–insertion copolymerization of propylene with disubstituted polar olefins. In addition, the thermal properties of the obtained copolymers were evaluated by the DSC analyses.

Kinetics controlled microstructure and composition in coordinative chain transfer copolymerization of ethylene–propylene

The wide applications of ethylene–propylene copolymers, which range from elastomers to oligomeric lubricants and additives can be expanded upon controlling the microstructure specifically its chemical composition. To account for that we use rac-Et(Ind)2ZrCl2 metallocene catalyst in combination with modified methylaluminoxane (MMAO) as the cocatalyst and ZnEt2 as the chain transfer agent (CTA) in a coordinative chain transfer copolymerization. The monotonic decline of molar mass and narrowing of its distribution in the presence of CTA suggest the establishment of the regenerative chain transfer reaction. The end-group analysis by 1H NMR spectroscopy demonstrates the depletion of β-H transfer and replacement of chain transfer to CTA. Microstructure analysis of copolymers by 13C NMR reveals a significant increase in ethylene content, which raises smoothly by CTA content, along with modification of the microstructure at the triad level, suggesting the prevalence of ethylenic sequences. This is in line with the decrease of the glass transition temperature and appearance of a broad melting peak between 30 and 90 °C. We explain these experimental observations by a computational study at the DFT level that compares three reaction pathways of ethylene and propylene insertion into an ethylene-ended propagating chain or chain transfer to the CTA. The outcome shows that propylene insertion is kinetically less feasible compared to ethylene insertion or chain transfer, while thermodynamically the chain transfer reaction is less favored. These results establish a new kinetics control over the chain microstructure in ethylene–propylene copolymers.

Furan as Impurity in Green Ethylene and Its Effects on the Productivity of Random Ethylene-Propylene Copolymer Synthesis and Its Thermal and Mechanical Properties.

The presence of impurities such as H2S, thiols, ketones, and permanent gases in propylene of fossil origin and their use in the polypropylene production process affect the efficiency of the synthesis and the mechanical properties of the polymer and generate millions of losses worldwide. This creates an urgent need to know the families of inhibitors and their concentration levels. This article uses ethylene green to synthesize an ethylene-propylene copolymer. It describes the impact of trace impurities of furan in ethylene green and how this furan influences the loss of properties such as thermal and mechanical properties of the random copolymer. For the development of the investigation, 12 runs were carried out, each in triplicate. The results show an evident influence of furan on the productivity of the Ziegler-Natta catalyst (ZN); productivity losses of 10, 20, and 41% were obtained for the copolymers synthesized with ethylene rich in 6, 12, and 25 ppm of furan, respectively. PP0 (without furan) did not present losses. Likewise, as the concentration of furan increased, it was observed that the melt flow index (MFI), thermal (TGA), and mechanical properties (tensile, bending, and impact) decreased significantly. Therefore, it can be affirmed that furan should be a substance to be controlled in the purification processes of green ethylene.

Optimizing the removal of calcium and magnesium from synthetic reverse osmosis concentrate using functional polyketones: A combined experimental and machine learning approach

In this study, we synthesized functional polyketones (FPKs) for removing scaling ions (Ca2+ and Mg2+) from synthetic reverse osmosis concentrate (ROC) and optimized the adsorption processes using experimental and machine learning (ML) techniques, including gene expression programming (GEP) and multilayer perceptron (MLP) modeling. PK30 (a copolymer of ethylene and propylene with carbon monoxide) was reacted with four different amines, including 1,2-diaminopropane (DAP), 1-(2-aminoethyl) piperazine (AEP), butylamine (BA), and 1-(3-aminopropyl) imidazole (API), to produce FPKs. The effects of various factors, such as the amount of FPKs, synthetic ROC concentration, and pH, were investigated to optimize the removal of scaling ions from the synthetic ROC using novel GEP and MLP ML models. The experimental results revealed that Ca2+ and Mg2+ ions might be adsorbed primarily via the chelating mechanism. Increasing FPKs amounts and higher pH levels improved the adsorption process, with even low concentrations of FPKs demonstrating enhanced adsorption. The adsorption of the scaling ions followed the order API > AEP > BA > DAP, with removal percentages of 88.9, 87.3, 83.7, and 83.0 %, respectively. The MLP model outperformed the GEP model in optimizing Ca2+ and Mg2+ adsorption from the synthetic ROC and produced favorable results for all selected amines by determining the input-output relationship for the testing dataset with R2 = 0.806, 0.759, 0.760, and 0.878 for AEP, DAP, API, and BA, respectively. Overall, this study provides a viable solution for the pretreatment of ROC to remove scaling ions, which can improve the performance of zero liquid discharge systems by decreasing energy consumption.

Manual applied polyurethane-urea: High performance coating based on CO2-based polyol and polyaspartic ester

Brushable polyurea based on slow reactive process was prepared by simple, mild and solvent-free method. Firstly, polyurethane prepolymer was synthesized from poly (propylene carbonate) diol (PPCD, copolymer of propylene oxide/CO2) and 4,4′-dicylocyhexylmethane diisocyanate (HMDI). Polyurethane-urea (PPCD–PUU) was then obtained by the chain extension of prepolymer with polyaspartic ester (PAE). The mechanical properties of PPCD–PUU were optimized by adjusting the content of –NCO in the prepolymer and the ratio of prepolymer to PAE. The mechanical strength, thermal resistance, solvent resistance and hydrolysis resistance of PPCD–PUU were compared with those of PUUs derived from polypropylene glycol and poly-caprolactone diol. The results showed that the comprehensive mechanical properties of PPCD–PUU were balanced when the R value was 1.15 and the content of –NCO was 8 %. The tensile strength was 20.5 MPa, the elongation at break was 352 %, and the Young's modulus was 168.2 MPa. Especially, after soaking in 10 % H2SO4 aqueous solution, 10 % NaOH aqueous solution and 10 % NaCl aqueous solution for 24 h, the tensile properties were basically unchanged. Manual applied polyurethane-urea based on commercial PPCD has broad application prospects because it avoids the use of expensive spraying equipment.

Modeling of the Copolymerization of Propylene with 1‐Hexene to Predict the Copolymer Molecular Weight and Composition

AbstractA detailed mathematical model of the propylene‐1‐hexene copolymerization based on the two‐dimensional probability generation function technique is developed. It calculates the joint molecular weight‐copolymer composition distribution (MWD‐CCD) of the copolymer, as well as the average copolymer composition distribution, the molecular weight distribution (MWD), the copolymer composition distribution (CCD), average molecular weights and composition, and yield. The parallelized execution of the model code allows for obtaining the different copolymer microstructure distributions efficiently. The model allows for reaching a thorough understanding of the copolymer microstructure under different operating conditions of a semibatch reactor. It also has the potential to become a powerful tool for selecting operating conditions to obtain a material with target molecular properties.

Copolymerization of ω‐Alkenyltrimethylsilane/Propylene with Heterogeneous Ziegler‐Natta Catalyst: How Dose Alkenyl Length Affect Comonomer Incorporation?

AbstractThree ω‐alkenyltrimethylsilanes of different alkenyl moieties, i.e., 3‐butenyltrimethylsilane, 5‐hexenyltrimethylsilane, and 7‐octenyltrimethylsilane, are copolymerized with propylene over a heterogeneous Ziegler‐Natta catalyst. The experimental results reveal that, at odds with what the molecular volumes will foretell, 5‐hexenyltrimethylsilane top the three ω‐alkenyltrimethylsilanes in incorporation rate into PP while 3‐butenyltrimethylsilane becomes the most sluggish of the three. This comonomer incorporation rate order is in line with that of ω‐alkenylmethyldichlorosilanes in copolymerization with propylene‐synthesizing long‐chain‐branched PP (LCB‐PP), pointing to a peculiar alkenyl length effect on comonomer incorporation rate for these comonomers. DFT simulation is then applied to seek energetic basis in coordination‐insertion for such an effect. It is revealed that complexation abilities of the three ω‐alkenyltrimethylsilanes decrease in the following order: 3‐butenyltrimethylsilane > 5‐hexenyltrimethylsilane > 7‐octenyltrimethylsilane, in line with their molecular sizes. However, the insertion energy barriers increase in the order of: 5‐hexenyltrimethylsilane < 7‐octenyltrimethylsilane < 3‐butenyltrimethylsilane. The repulsive interaction between the bulky trimethylsilane functionality of ω‐alkenyltrimethylsilanes and growing PP chain is found to contribute significantly to the insertion energy barrier, which grows disproportionally large with 3‐butenyltrimethylsilane. The current discovery will be conducive to understanding the more complex ω‐alkenylmethyldichlorosilane/propylene copolymerization that synthesizes the industrially important LCB‐PP.