Chain Growth Research Articles

CO2 Hydrogenation: Na Doping Promotes CO and Hydrocarbon Formation over Ru/m-ZrO2 at Elevated Pressures in Gas Phase Media.

Sodium-promoted monoclinic zirconia supported ruthenium catalysts were tested for CO2 hydrogenation at 20 bar and a H2:CO2 ratio of 3:1. Although increasing sodium promotion, from 2.5% to 5% by weight, slightly decreased CO2 conversion (14% to 10%), it doubled the selectivity to both CO (~36% to ~71%) and chain growth products (~4% to ~8%) remarkably and reduced the methane selectivity by two-thirds (~60% to ~21%). For CO2 hydrogenation during in situ DRIFTS under atmospheric pressure, it was revealed that Na increases the catalyst basicity and suppresses the reactivity of Ru sites. Higher basicity facilitates CO2 adsorption, weakens the C-H bond of the formate intermediate promoting CO formation, and inhibits methanation occurring on ruthenium nanoparticle surfaces. The suppression of excessive hydrogenation increases the chain growth probability. Decelerated reduction during H2-TPR/TPR-MS and H2-TPR-EXAFS/XANES at the K-edge of ruthenium indicates that sodium is in contact with ruthenium. A comparison of the XANES spectra of unpromoted and Na-promoted catalysts after H2 reduction showed no evidence of a promoting effect involving electron charge transfer.

MOF-Derived Ru1Zr1/Co Dual-Atomic-Site Catalyst with Promoted Performance for Fischer-Tropsch Synthesis.

Cobalt-based catalysts have been widely used for Fischer-Tropsch synthesis (FTS) in industry; however, achieving rational catalyst design at the atomic level and thereby a higher activity and more long-chain-hydrocarbon products simultaneously remain an attractive and difficult challenge. The dual-atomic-site catalysts with unique electronic and geometric interface interactions offer a great opportunity for exploiting advanced FTS catalysts with improved performance. Herein, we designed a Ru1Zr1/Co catalyst with Ru and Zr dual atomic sites on the Co nanoparticle (NP) surface through a metal-organic-framework-mediated synthesis strategy which presents greatly enhanced FTS activity (high turnover frequency of 3.8 × 10-2 s-1 at 200 °C) and C5+ selectivity (80.7%). Control experiments presented a synergic effect between Ru and Zr single-atom site on Co NPs. Further density functional theory calculations of the chain growth process from C1 to C5 revealed that the designed Ru/Zr dual sites remarkably lower the rate-limiting barriers due to the significantly weakened C-O bond and promote the chain growth processes, resulting in the greatly boosted FTS performance. Therefore, our work demonstrates the effectiveness of dual-atomic-site design in promoting the FTS performance and provides new opportunities for developing efficient industrial catalysts.

Sustainability in Supply Chains through Rapid Capacity Increases and Minimized Disruptions

We examine the impediments to rapid recovery from a supply chain disruption through rapid supply chain growth in capacity. We explore how to minimize the effects of disruptions in supply chains that could be caused by pandemics, wars, supplier down times, absenteeism, distributor bottlenecks, etc. The tools we use include reliability theory, logic, simulation, and other methodologies. Our objective is to better understand supply chain disruptions and to propose solutions to the sustainability problems currently being experienced within supply chains. The authors use models to better comprehend how to avoid supply chain structures that are easily disrupted. Included among the findings are that disruptions cause the loss of production capacity; thus, the ability to rapidly increase production capacity in the same or other parts of the supply chain becomes paramount. Furthermore, structural redundancy can help alleviate the loss of capacity coming from a disruption. One purpose of the models is to foster a basic appreciation for the different lead times and fixed costs associated with capacity expansion of the various supply chain components. There are implications for where within the supply chain additional robustness and capacity are needed.

The COVID-19 pandemic and supply chain: international cooperation patterns and influence mechanism

PurposeThe aim of this study is to undertake a systematic analysis of the supply chain literature to uncover the changes and patterns of international cooperation in the context of the COVID-19 pandemic.Design/methodology/approachIn this study, the information on supply chain-related publications in the Web of Science (WOS) database is analyzed using statistical techniques and visual approaches. The focus is on the five countries with the highest number of supply chain publications, accounting for approximately 70% of global publications. This in-depth analysis aims to provide a clearer understanding of the cooperation patterns and their impact on the supply chain during the COVID-19 pandemic.FindingsThe results of the study reveal that the growth rate of international cooperation in supply chain research during the COVID-19 pandemic is higher compared to the 5-year and 10-year periods before the pandemic. This suggests that the pandemic has not hindered international cooperation in the field, but instead has increased collaboration. In terms of international cooperation patterns, the findings indicate that China and the USA have a strong partnership, with China being the largest partner for the USA and vice versa. The UK's largest partner is China, India's largest partner is the UK and Italy's largest partner is also the UK. This implies that trade, rather than the pandemic, is a determining factor in supply chain research.Research limitations/implicationsThis study examines the patterns of international cooperation in supply chain research during the COVID-19 pandemic, providing insights into the changes and mechanisms of international cooperation in this field. Moreover, the results of this study may offer practical benefits for supply chain operators and managers. By providing a deeper understanding of the international cooperation patterns in the field, this research could contribute to the recovery and growth of the global supply chain.Social implicationsThis study's analysis of the impact of crisis events, such as the COVID-19 pandemic, on international cooperation in supply chain research contributes to the theoretical development of the field. Additionally, by examining how academia responds to emergencies, it provides valuable insights for operations and supply chain managers in their pursuit of more effective supply chain management.Originality/valueThis study provides a preliminary examination of the international cooperation patterns of supply chain research in the context of the COVID-19 pandemic, representing a novel and early contribution to the existing literature, helping to expand upon current understanding in the field and provide a more comprehensive perspective. Furthermore, this study offers a practical analysis strategy for future supply chain research, fostering progress and growth in the field.

Investigation of Al precursor for ethanol synthesis from syngas on Cu-based multifunctional catalyst

The use of cheap Cu-based catalyst to directly synthesize ethanol and higher alcohols from syngas has been favored by researchers. However, the role of Al-based components and carbon chain growth are still unclear. Herein, a series of Cu-based multifunctional catalysts prepared by various Al precursors using complete liquid phase method are investigated for ethanol and higher alcohols synthesis. It is found that the catalysts using aluminium isopropoxide and Al2O3 as the Al precursor exhibit comparable activity with about 20% of CO conversion, 27% of ROH selectivity and >50% of C2+OH selectivity. Results show that different Al precursors can simultaneously adjust the ratios of Cu+/(Cu++Cu0) and the amount of weak acid on catalyst surface, thus leading to various concentration of CHn⁎/CHxO⁎ on catalyst surface. In-situ DRIFT experiment indicates that a strong intensity of bridge-adsorbed of CO occurs over slurry ternary CuZnAl catalysts, which facilitates the cleavage of CO bond and consequently favors the formation of CHn⁎ key intermediates. Moreover, we have found that the carbon chain growth can be proceeded by the C-C coupling of CHn⁎ and CHxO⁎, or via CO⁎ insert into CHn⁎ to form CHnCHxO⁎/CHnCO⁎ which is further hydrogenated to form ethanol and higher alcohols.

Identifying the Performance Descriptor in Direct Syngas Conversion to Long-Chain α-Olefins over Ruthenium-Based Catalysts Promoted by Alkali Metals

Fischer-Tropsch synthesis (FTS) provides a nonpetroleum route for the production of value-added α-olefins from syngas. However, regulating the product distribution to promote the formation of long-chain α-olefins while maintaining low selectivity to C1 byproducts (CO2 and CH4) remains a great challenge. Herein, a series of alkali metal-promoted Ru/SiO2 catalysts were synthesized to investigate the effect of alkali metals and identify the performance descriptor for syngas to α-olefins. X-ray absorption and photoelectron spectroscopy as well as CO diffuse reflectance infrared Fourier transformation spectra revealed that Ru’s electronic structure can be tuned by the addition of alkali metal promoters. The Allen scale electronegativity deviation between the metallic Ru and the alkali metal promoter, which was identified as a performance descriptor, was correlated with the initial turnover frequency (TOF) and olefins distribution, as well as the chain growth probability. In addition, the fraction of olefin products was successfully adjusted from lower olefins (50.3%) to long-chain α-olefins (85.8%) by controlling the kinds of alkali metal promoters. Evidences from X-ray absorption spectroscopy and chemisorption characterizations revealed that the controllable Ru electron density could enhance CO adsorption and hinder the reactivity of chemisorbed H species, thus benefiting the α-olefin production. These results offer a comprehensive view of the electronic effect for regulating product selectivity during the Fischer-Tropsch reaction process.

Tuning Fischer-Tropsch synthesis product distribution toward light olefins over nitrided Fe-Mn bimetallic catalysts

A series of Fe-Mn bimetallic catalysts with various pretreatment atmosphere including H2, CO and alternatively NH3, were employed for the Fischer–Tropsch synthesis (FTS). The structure of Fe-Mn bimetallic catalysts was revealed by using multiple characterization techniques, where Mössbauer spectra was used to define the iron species. With direct pretreatment, the reduction efficiency is in the sequence of H2 > CO > NH3. Fe-Mn bimetallic catalysts pre-reduced by H2 that permit an easy nitrogenation. To correlate the phase compositions of spent catalysts with FTS performance, the individual contribution of Fe, iron carbides (χ-Fe5C2, ε-Fe2(.2)C and θ-Fe3C) and iron nitride (Fe2N) to hydrocarbon selectivity was deconvolved by linear regression. It was discovered that C2=-C4= selectivity was proportional to the content of epsilon-iron carbide, which was promoted by the doping with Mn and further nitriding treatment. Successfully nitrided Fe-Mn bimetallic catalysts exhibit a better stability of C2-C4 O/P along time on stream, while either direct CO treatment or NH3 treatment followed by CO treatment result in a rapid decent of C2-C4 O/P ratio against time. Furthermore, Mn enhances long-chain hydrocarbon selectivity and suppresses CH4 formation, whereas the nitrogenation inhibits the chain growth ability, concentrating the hydrocarbon selectivity into C2-C4 fraction. Hence, the nitrided Fe-Mn catalyst is able to maintain a high light olefin selectivity. This study highlights that nitrogenation could provide an opportunity to tune the C2-C4 olefins by optimizing the phase structure of Fe-Mn catalysts.

Value chain, regional institutions and firm growth in Europe

AbstractWe analyse whether and to what extent the quality of regional institutions has a differential effect on firms’ growth driven by heterogeneity in firm value chain positioning. We analyse turnover growth during the period 2010–2013 for a sample of manufacturing firms located in four European countries—France, Germany, Italy and Spain. We distinguish final firms serving end markets from suppliers serving other firms. Our instrumental variable estimates point to high-quality regional institutions enhancing the growth performance of only locally embedded suppliers with operations confined to the own regional market—that is, the ‘weakest’ node of the value chain.

Fabrication of Transition Metal (Mn, Co, Ni, Cu)‐Embedded Faveolate ZnFe2O4 Spinel Structure with Robust CO2 Hydrogenation into Value‐added C2+ Hydrocarbons

AbstractCO2 hydrogenation is the most efficient way to achieve the goal of “Carbon Neutral,” and the transition metals (Mn, Co, Ni, Cu)‐embedded faveolate ZnFe2O4 were fabricated and then evaluated with a CO2 hydrogenation test. The systematic investigation of the effect of the introduced transition metals on the catalytic performance revealed that the activity was influenced by the surface structure, especially by the surface Fe−C percentages. The introduction of Zn could increase CO2 adsorption, thus promoting the reverse water gas shift (RWGS) reaction, which is considered the first step during CO2 hydrogenation. The surface Fe−C species played a significant role during the Fischer‐Tropsch (F−T) synthesis, specific to the carbon chain growth process. Among all catalysts, Co‐doped ZnFe2O4 exhibited the highest surface Fe−C percentage; therefore, it exhibited the optimal CO2 conversion, C2+ selectivity, C2‐C4 space‐time yield, and olefin/paraffin ratio, which were 42.12 %, 81.26 %, 34.64 %, and 40.25 %, respectively. Furthermore, the introduced Co species can also act as active sites to enhance the activation and dissociation of CO2, as confirmed by theoretical adsorption calculations.

Asymmetric Ion-Pairing in Stereoselective Vinyl Polymerization

Controlling polymer tacticity is a key consideration in macromolecular synthesis due to the impact of stereochemistry on a material’s thermomechanical and optical properties. Recently, inspired by work in small molecule catalysis, asymmetric ion-pairing has emerged as a valuable approach to control the stereochemistry of polymers made through chain growth polymerization of vinyl monomers. This Perspective outlines some of the challenges inherent to polymer stereocontrol as well as highlights recent catalyst development in the area of asymmetric ion-pairing that has enabled control of both the configuration and conformation of vinyl polymers. Several synthetic opportunities and mechanistic questions have been identified that will expand the impact of asymmetric ion-pairing in polymer synthesis.

Toward Defect Suppression in Polythiophenes Synthesized by Direct (Hetero)Arylation Polymerization

In this study, we have investigated different reaction conditions for defect suppression in polythiophene derivatives synthesized by direct (hetero)arylation polymerization (DHAP). The well-known PQT12 polymer was used as a model due to its simple structure which facilitated analysis. 2-Bromo-3,4′-didodecyl-2:2′,5′:2″,5″:2‴-quaterthiophene and 2-bromo-3″,4‴-didodecyl-2:2′,5′:2″,5″-2‴-quaterthiophene monomers allowed the analysis of both homocoupling defects and β-branching defects due to their asymmetric structure as well as the effect of β-protection. The properties of the resulting polymers were analyzed using size-exclusion chromatography, differential scanning calorimetry, UV–visible absorption spectroscopy, and 1H NMR spectrometry. Some model compounds were synthesized to help with end-groups analysis, revealing debromination as the main obstacle to chain growth. The highest quality polymer was obtained when using toluene as a solvent, Pd2dba3 as a palladium(0) catalyst, neo-decanoic acid (NDA) as a carboxylic acid additive, and a dual-ligand system with diamine TMEDA and phosphine P(o-OMePh)3. This study also revealed the importance of the choice of the monomers for the preparation of well-defined conjugated polymers.

Stochastic Modelling and Simulation of Free Radical Polymerization of Styrene in Microchannels using a Hybrid Gillespie Algorithm

Most recently, the production of polystyrene by Free Radical Polymerization (FRP) via microchannels has been a subject of core interest due to the efficiency of a micro-or milli-reactor brings. In addition, especially in pilot experimentations, a micro or milli-reactor has been known widely to be efficient in monitoring the microstructural end-use features or properties of the polymer as the chain propagates and ultimately terminates. However, the limitations posed by using micro or milli-reactors in process intensification such as clogging of pores can be a bottleneck when tracking the common phenomena associated with FRP such as cage, gel, and glass effects. In this work, the simulation of the synthesis of polystyrene in FRP via microchannels is computed using a robust and time-efficient hybrid Gillespie Algorithm (GA) or Hybrid Stochastic Simulation Algorithm (HSSA). The obtained results of the end-use properties of polystyrene such as Monomer conversion, Polydispersity Index, Number-Average Molar Mass and Weight Average Molar Mass were compared to experimental data. The simulation results agree well with the experimental results reported in this work. Hence, stochastic simulations prove to be an effective tool in making decisions in the context of process intensification of chain growth polymerization reactions even at a large scale.

Effects of additives on properties of self-skinning polyurethane foam for automobile steering wheel

Commercialized polyurethane foam products for automobile steering wheels have been committed to the development of products with comprehensive properties such as low density, high production efficiency and environmental protection. Based on this, this article has launched a series of experiments to explore the effects of different types of chain extenders, blowing agents and catalysts on the mechanical properties, cell structure, skin and reactivity of self-skinning polyurethane foams for automobile steering wheels. The results show that the hardness and tensile strength of the foam gradually decrease with the chain growth of small molecular chain extenders (ethylene glycol, 1.3-propanediol, 1.4-butanediol), and the elongation at break increases gradually. The foaming agent formic acid is more conducive than water as it favors the formation of small but compact cells, thus dense skin. The catalytic efficiency of non-reactive catalysts (A1, KC101 and DabcoEG) is higher than that of reactive catalysts (LED-103, ZR-50, DPA). The theoretical research for the development of high-performance and high-efficiency polyurethane foam products for automobile steering wheels.

Supramolecular Polymer Brushes.

Polymer brushes are thin polymer films that consist of densely grafted, chain-end tethered polymers. These thin polymer films can be produced either by anchoring presynthesized chain-end functional polymers to the surface of interest ("grafting to"), or by using appropriately modified surfaces to facilitate growth of polymer chains from the substrate ("grafting from"). The vast majority of polymer brushes that have been prepared and studied so far involved chain-end tethered polymer assemblies that are anchored to the surface via covalent bonds. In contrast, the use of noncovalent interactions to prepare chain-end tethered polymer thin films is much less explored. Anchoring or growing polymer chains using noncovalent interactions results in supramolecular polymer brushes. Supramolecular polymer brushes may possess unique chain dynamics as opposed to their covalently tethered counterparts, which could provide avenues to, for example, renewable or (self-)healable surface coatings. This Perspective article provides an overview of the various approaches that have been used so far to prepare supramolecular polymer brushes. After presenting an overview of the various approaches that have been used to prepare supramolecular brushes via the "grafting to" strategy, examples will be presented of strategies that have been successfully applied to produce supramolecular polymer brushes via "grafting from" methods.

Mass spectrometry insight into the electro-copolymerization mechanism of aniline with o-phenylenediamine

It has been a challenge to accurately characterize the chain growth mechanism during copolymerization. Herein, an electrochemistry-microtube-mass spectrometry (EC-mTube-MS) was developed for on-line monitoring of aniline (ANI) electro-copolymerized with o-phenylenediamine (oPD). Short-lived intermediates and co-oligomers belonging to polyANI-oPD were structural identified with tandem MS method for the first time. The free binding between ANI and oPD monomers determined the presence of more species for a given co-n-mer. Chain growth was found to compete with 2H+, 2e− intramolecular oxidation of co-oligomers, resulting in the units with quinone or phenazine structures. MS signals for polyANI and polyoPD were observed as well, indicating that the homopolymerization occurred simultaneously with the copolymerization, which may affect the formation efficiency even performance of the final copolymer. Investigations on the monomer feed ratio and solution pH provided data support for improving the copolymerization efficiency, and the recommended parameters are cANI: coPD ≥ 10:1 and pH = 7.

Insights into the Fischer–Tropsch mechanism on χ-Fe5C2(510) based on the hydrogen coverage effect

Investigating the mechanism of the Fischer–Tropsch synthesis is beneficial for modifying catalysts, which would result in an improved catalyst performance. However, theoretical calculations have mainly focused on several key elementary reactions and have thus provided fragmented information. Here, we select χ-Fe5C2(510) as representative facet and consider the elementary reactions on as comprehensively as possible via the density-functional theory (DFT)-based kinetic Monte Carlo (kMC) method to generate the fine structure of the Fischer–Tropsch mechanism. The results reveal that the CO activation mechanism is divided into cyclical pathways and termination pathways. The chain growth process and chain dissociation process coexist in the Fischer-Tropsch synthesis while the former follows the CO insertion mechanism, and the latter follows the carbide mechanism. The product methane and ethylene are produced major from the intermediates which are generated in the chain dissociation process rather than the chain grown process as the article reported before. The deep interpretation of the Fischer–Tropsch mechanism from the fine structure could be the guidance to experimentalists in mechanism verification or catalyst design.

Amide-Functionalized Polyolefins and Facile Post-Transformations

Direct copolymerization of olefins with polar monomers to produce functionalized polyolefins has attracted much attention; however, highly efficient incorporation of amide functions into polyolefins is a long-standing challenge because the amide function is pronounced to retard chain growth. In this contribution, Vince Lactam’s derivatives (VLH, VLMe, and VLBoc) that contain high ring strain and an amide moiety are utilized in ethylene copolymerization mediated by palladium catalysts. Amide-functionalized polyethylenes, poly(E-VLBoc)s, are accessible with key characteristics of high amide incorporations (up to 30.1 mol %), high copolymer molecular weights, and high catalytic activities. The incorporation of the amide comonomer converts crystalline poly(E-VLBoc)s (Tm = 115–125 °C) to noncrystalline and transparent poly(E-VLBoc)s (Tg = 98–196 °C, optical transmittance (T) = 87.6%–90.4%). Both characteristics of cyclic amide functions and high amide incorporations in poly(E-VLBoc) enable facile post-transformations under mild conditions to produce hydrogen bond-containing (-C(O)NH-) poly(E-VLH), difunctionalized (-COOH and -NHR) poly(E-VLNHBoc), and water-soluble ammonium-functionalized poly(E-VLNH3+). The ammonium functionality endows polyolefin with antibacterial properties.

Molecular basis of polyglutamine-modulated ELF3 aggregation in Arabidopsis temperature response.

Some plants, like Arabidopsis thaliana, possess a molecular mechanism that allows them to sense changes in temperature and respond by modifying growth rate, photoperiod length and timing of flowering. Underlying this mechanism is a tripartite protein complex called the Evening Complex (EC) that functions as a DNA transcription repressor targeting growth-related genes. ELF3, a large disordered scaffolding protein, is the primary component of the EC. At low temperature ELF3 sits over DNA targets occluding transcription machinery and halting growth. Rising temperature promote ELF3 condensate formation as it becomes sequestered in large reversible nuclear condensates allowing DNA transcription and plant growth to proceed. A C-terminal prion-like domain (PrD) has been observed to be sufficient for ELF3 aggregation. Within this PrD region lies a poly-glutamine repeat of variable length, the size of which has been found to modulate the thermal responsiveness as measured by hypocotyl (stem) elongation and condensate formation. We use a polymer chain growth approach to build large ensembles and characterize monomeric ELF3-PrD at a range of polyQ lengths and temperatures. We then explore temperature-dependent dynamics of wild-type ELF3-PrD and a mutant, F527A, using chain growth structures as initial conformations for replica exchange (REST2) simulations. We find increased solvent accessibility of expanded polyQ tracts, promotion of temperature-sensitive helices adjacent to polyQ tracts, and exposure of a cluster of aromatic residues at increased temperature, all three of which promote inter-protein interaction. Protein condensate formation is a ubiquitous but poorly understood mechanism implicated in a range of biological functions and malfunction. Our computational approach to understanding the molecular basis for the temperature sensitivity of this system has wider implications on the understanding of phenomena regulating condensate formation more generally.

Advances in the One-Step Approach of Polymeric Materials Using Enzymatic Techniques.

The formulation in which biochemical enzymes are administered in polymer science plays a key role in retaining their catalytic activity. The one-step synthesis of polymers with highly sequence-controlled enzymes is a strategy employed to provide enzymes with higher catalytic activity and thermostability in material sustainability. Enzyme-catalyzed chain growth polymerization reactions using activated monomers, protein-polymer complexation techniques, covalent and non-covalent interaction, and electrostatic interactions can provide means to develop formulations that maintain the stability of the enzyme during complex material processes. Multifarious applications of catalytic enzymes are usually attributed to their efficiency, pH, and temperature, thus, progressing with a critical structure-controlled synthesis of polymer materials. Due to the obvious economics of manufacturing and environmental sustainability, the green synthesis of enzyme-catalyzed materials has attracted significant interest. Several enzymes from microorganisms and plants via enzyme-mediated material synthesis have provided a viable alternative for the appropriate synthesis of polymers, effectively utilizing the one-step approach. This review analyzes more and deeper strategies and material technologies widely used in multi-enzyme cascade platforms for engineering polymer materials, as well as their potential industrial applications, to provide an update on current trends and gaps in the one-step synthesis of materials using catalytic enzymes.

Ring-Opening Polymerization of rac-Lactide Catalyzed by Octahedral Nickel Carboxylate Complexes

To date, nickel(II) complexes have not been practically investigated as catalysts in ring-opening polymerization (ROP) of lactide to produce biodegradable poly(lactic acid), which is in demand in biomedicine and industry. In this study, carboxylate complexes of nickel(II) containing various N-donor ligands with different nuclearity, metal core rigidity and nature of carboxylate ligands were synthesized and studied by infrared spectroscopy, X-ray diffraction, elemental and thermogravimetric analyses. The obtained complexes were examined in the ROP of the rac-lactide in bulk and in toluene solution with and without the addition of a benzyl alcohol initiator. In the series of complexes studied, the complex [Ni(DBED)2(O2CC(CH3)3)2]·(CH3)3CCO2H (DBED is N,N′-dibenzylethylenediamine) was a syndioselective catalyst and showed the highest catalytic ability in the polymerization without the addition of benzyl alcohol. For this complex, according to 1D DOSY 1H NMR spectroscopy and mass spectrometry with electrospray ionization, polymerization is initiated by a free secondary amine, DBED, leaving the metal’s inner coordination sphere. Based on the experimental data obtained, a comprehensive density functional theory (DFT) study of the ROP pathways including the initiation and first chain growth cycle steps with a detailed description of the intermediates and evaluation of the energy barriers of the steps was carried out. It was shown that one of the key roles in the reaction process is played by carboxylate ligands, which act as proton carriers from the initiator molecule and have a significant influence on the reactivity of the catalytic metal complexes.