Coordinative Chain Transfer Polymerization Research Articles

IPP/PE Multiblock Copolymers for Plastic Blend Recycling Synthesized by Coordinative Chain Transfer Polymerization

Recycling of blends of widely used plastics is a key challenge of the envisioned circular economy, and thus, protocols permitting the efficient synthesis of effective compatibilizers are highly desirable. We report herein that coordinative chain transfer polymerization permits the efficient one-pot synthesis of multiblock architectures of strictly linear polyethylene or high-density polyethylene (HDPE) and isotactic polypropylene (iPP). Various block copolymers having an iPP backbone and HDPE side chains were synthesized and used to compatibilize HDPE/iPP plastic blends. The synthesized block copolymers differ in their overall molecular weights and have different HDPE side chain lengths and numbers. A block copolymer with a molecular weight of Mp = 33,700 g × mol–1 including 4.5 HDPE side chains with a molecular weight of Mn = 600 g × mol–1 showed the highest efficiency for compatibilizing 30/70 wt % blends of HDPE/iPP with a 5 wt % compatibilizer addition. This block copolymer is also superior to commercially available compatibilizers.

Influence of external N‐containing donors on the neodymium‐based catalytic system for 1,3‐butadiene polymerization

AbstractEvaluation of the heteroatom tolerance capability of neodymium‐based precatalysts and its accompanied catalytic influences is of great significance for industrial production of polybutadienes because the corresponding active species is highly sensitive to heteroatom‐based impurities that are usually inevitable in the polymerization system. Based this consideration, the present research disclosed a systematical study of the influence of N‐containing donors on a ternary Nd‐based system of Nd(vers)3/DIBAH/TEA/EASC. It was found that the presence of 1% of such donors, regardless of their types that bears different electronic/steric properties, brought little influence on the catalytic activities as well as the cis‐1,4‐stereoselectivities of the catalytic system, giving cis‐1,4‐enriched polybutadienes with comparable yields. Furthermore, the presence of such a concentration of N‐donor also brought little influence on the coordinative chain transfer polymerization behaviors of the system, giving narrowly distributed polybutadiene products in a well‐controlled manner. Nevertheless, further increasing the concentration of N‐donors to >1% eventually led to a gradually decreased polymer yields due to the poison of the corresponding active species, and the obtained catalytic efficiencies were highly dependent on the types of N‐donors. The influence of the N‐donor on other parameters of the products, that is, molecular weights, polydispersities, and so forth, were also investigated, and the specific reasons were proposed.

Coordinative Chain Transfer Polymerization of Sustainable Terpene Monomers Using a Neodymium-Based Catalyst System.

The present investigation involves the coordinative chain transfer polymerization (CCTP) of biobased terpenes in order to obtain sustainable polymers from myrcene (My) and farnesene (Fa), using the ternary Ziegler–Natta catalyst system comprising [NdV3]/[Al(i-Bu)2H]/[Me2SiCl2] and Al(i-Bu)2H, which acts as cocatalyst and chain transfer agent (CTA). The polymers were produced with a yield above 85% according to the monomeric consumption at the end of the reaction, and the kinetic examination revealed that the catalyst system proceeded with a reversible chain transfer mechanism in the presence of 15–30 equiv. of CTA. The resulting polyterpenes showed narrow molecular weight distributions (Mw/Mn = 1.4–2.5) and a high percent of 1,4-cis microstructure in the presence of 1 equiv. of Me2SiCl2, having control of the molecular weight distribution in Ziegler–Natta catalytic systems that maintain a high generation of 1,4-cis microstructure.

Preparation of Well-Controlled Isotactic Polypropylene-Based Block Copolymers with Superior Physical Performance via Efficient Coordinative Chain Transfer Polymerization

Preparation of Well-Controlled Isotactic Polypropylene-Based Block Copolymers with Superior Physical Performance via Efficient Coordinative Chain Transfer Polymerization

Terpene Coordinative Chain Transfer Polymerization: Understanding the Process through Kinetic Modeling.

The interest in the Coordinative Chain Transfer Polymerization (CCTP) of a family of naturally occurring hydrocarbon monomers, namely terpenes, for the production of high-performance rubbers is increasing year by year. In this work, the synthesis of poly(β-myrcene) via CCTP is introduced, using neodymium versatate (NdV3), diisobutylaluminum hydrade (DIBAH) as the catalytic system and dimethyldichlorosilane (Me2SiCl2) as the activator. A bimodal distribution in the GPC signal reveals the presence of two populations at low conversions, attributable to dormants (arising from reversible chain transfer reactions) and dead chains (arising from termination and irreversible chain transfer reactions); a unimodal distribution is generated at medium and high conversions, corresponding to the dominant species, the dormant chains. Additionally, a mathematical kinetic model was developed based on the Method of Moments to study a set of selected experiments: ([β-myrcene]0:[NdV3]0:[DIBAH]0:[Me2SiCl2]0 = 660:1:2:1, 885:1:2:1, and 533:1:2:1). In order to estimate the kinetic rate constant of the systems, a minimization of the sum of squared errors (SSE) between the model predicted values and the experimental measurements was carried out, resulting in an excellent fit. A set of the Arrhenius parameters were estimated for the ratio [β-myrcene]0:[NdV3]0:[DIBAH]0:[Me2SiCl2]0 = 660:1:2:1 in a temperature range between 50 to 70 °C. While the end-group functionality (EGF) was predominantly preserved as the ratio [β-myrcene]0:[NdV3]0 was decreased, higher catalytic activity was obtained with a high ratio.

Preparation of star-shaped polybutadiene via coordinative chain transfer polymerization

Preparation of star-shaped polybutadiene via coordinative chain transfer polymerization

Switch from Anionic Polymerization to Coordinative Chain Transfer Polymerization: A Valuable Strategy to Make Olefin Block Copolymers.

Anionic polymerization of butadiene or/and styrene is performed with lithium initiators, functional or not. The polymer chains are subsequently transferred to magnesium. The resulting polymeryl-magnesium compounds were combined with {(Me2 Si(C13 H8 )2 )Nd(μ-BH4 )[(μ-BH4 )Li(THF)]}2 metallocene complex to act as macromolecular chain transfer agents (macroCTAs) in coordinative chain transfer polymerization (CCTP) of ethylene (E) or its copolymerization (CCTcoP) with butadiene (B). Block copolymers were produced for the first time by this switch from anionic polymerization to CCTP. Hard and soft blocks such as PB, polystyrene (PS), poly(styrene-co-butadiene) (SBR) obtained by anionic polymerization and PE or poly(ethylene-co-butadiene) (EBR) produced by CCT(co)P were combined and the corresponding structures were characterized.

Switch from Anionic Polymerization to Coordinative Chain Transfer Polymerization: A Valuable Strategy to Make Olefin Block Copolymers

AbstractAnionic polymerization of butadiene or/and styrene is performed with lithium initiators, functional or not. The polymer chains are subsequently transferred to magnesium. The resulting polymeryl‐magnesium compounds were combined with {(Me2Si(C13H8)2)Nd(μ‐BH4)[(μ‐BH4)Li(THF)]}2 metallocene complex to act as macromolecular chain transfer agents (macroCTAs) in coordinative chain transfer polymerization (CCTP) of ethylene (E) or its copolymerization (CCTcoP) with butadiene (B). Block copolymers were produced for the first time by this switch from anionic polymerization to CCTP. Hard and soft blocks such as PB, polystyrene (PS), poly(styrene‐co‐butadiene) (SBR) obtained by anionic polymerization and PE or poly(ethylene‐co‐butadiene) (EBR) produced by CCT(co)P were combined and the corresponding structures were characterized.

Amphiphilic olefin block copolymers synthesized by successive coordinative chain transfer and ring-opening polymerizations

Introducing polarity is a necessity for widening the application scope of polyolefins specifically for developing biocompatible products. To this end, we exploit a two-step polymerization process to synthesize poly(ethylene‑b‑caprolactone) PE‑PCL block copolymers, which contain both polar and non-polar segments. First ethylene is polymerized by a generic metallocene catalyst in the presence of ZnEt2 as the chain transfer agent according to the coordinative chain transfer polymerization (CCTP) technique. Terminal zinc atoms are subsequently replaced by hydroxyl groups (PE‑OH) by exposing dormant polymer chains to oxygen. Afterward, ring-opening polymerization (ROP) of ε‑caprolactone is initiated by PE‑OH to form PE‑PCL block copolymers. Successful formation of both blocks is verified by FTIR and NMR spectroscopy. The presence of PCL blocks greatly lowers the crystallinity of ethylene sequences according to XRD and DSC results. Moreover, a second type of PE crystals with more chain folds and lower lamella thickness is found in block copolymers, which is absent in the equivalent physical blend. The diverse crystal structure of block copolymers suggest that phase separation exists between PE and PCL segments. The SEM image of the equivalent physical blend confirms the tendency of PCL and PE chains to phase separate, and infers a compatibilization in the presence of PE‑PCL block copolymers. This phase separation is detected by rheological measurements, as well, where block copolymers show deviations from Maxwell behavior in the terminal relaxation zone at low frequencies. Rheology results also show that the order-disorder transition temperature (TODT) of these block copolymers is higher than 180 °C. These results provide a clear picture from the morphology and utility of such block copolymers specifically for compatibilizing blends of polar polymers and non-polar polyolefins, which significantly broaden the utility of polyolefins.

Olefin polymerization cocatalysts: Development, applications, and prospects

<p indent="0mm">The annual global production of polyolefin products exceeds 100 million tons, and they are widely used in various fields. In contrast to heterogeneous polymerization that produces polyolefins with broad dispersity, single-site transition-metal-catalyzed homogeneous olefin polymerization enables the synthesis of polyolefins with narrow molecular weight distribution, controllable chain segment length, and uniform insertion ratio. It can flexibly tune the molecular structure of polyolefins to provide polyolefin materials with the required properties, which can be applied to high-end applications such as medical packaging and medical equipment. It is important to choose a suitable combination of a catalyst and cocatalyst to obtain tailor-made polyolefins through high-efficiency homogeneous polymerization. The main function of the cocatalyst is to react with the catalyst precursor to generate and stabilize active metal cations, the latter being the center of catalyzing olefin polymerizations. This review summarizes the most important work regarding cocatalysts in the past two decades, including novel structures: Mono/dinuclear boron-, aluminum-, and polymer-based promoters. This review illustrates the importance of the weakly coordinative nature of the counter anion, providing the design principle for the development of a highly efficient cocatalyst. Activation mechanism: The use of an industrial catalysis-related pyridylamido hafnium complex is an example that showcases the complicated reactions of this catalyst with different cocatalysts, shedding light on the importance of choosing the pair of catalyst and cocatalyst. Applications in polymerization: Binuclear cocatalysts and the cocatalysts combined with coordination chain transfer polymerizations are used to synthesize novel structural polyolefins, indicating that the cocatalyst plays a crucial role in alternating polyolefin structures. Cocatalyst-involved catalyst deactivation reactions: This part emphasizes the reaction pathways of cocatalysts that lead to catalyst deactivation, including the replacement of metal and ligand. Further, this review proposes the possible future development of cocatalysts by investigating the reported compounds with high Lewis acidity and the development of novel functionalized cocatalysts. For instance, the development of external stimuli-responsive cocatalyst structures may be one of the future development directions. Combining cocatalysts with existing catalytic methods, such as the coordinative chain transfer polymerization for synthesizing polyolefins with a novel structure, may be the second development direction in the future. With the advancement of computer hardware and algorithms together with experimental data, computational chemistry helps understand the effect of cocatalysts on polymerization. Predicting the structure of new and efficient cocatalysts through big data and artificial intelligence is the third possible future development direction.

Design of selective divalent chain transfer agents for coordinative chain transfer polymerization of ethylene and its copolymerization with butadiene

A selective divalent chain transfer agent is designed to exclusively lead to polyolefin chain growth on a divalent pentanediyl moiety via coordinative chain transfer polymerization (CCTP).

Resolving long-chain branch formation in tandem catalytic coordinative chain transfer polymerization of ethylene via thermal analysis

Resolving long-chain branch formation in tandem catalytic coordinative chain transfer polymerization of ethylene via thermal analysis

Temporal Control over Two- and Three-State Living Coordinative Chain Transfer Polymerization for Modulating the Molecular Weight Distribution Profile of Polyolefins.

A highly versatile new strategy for manipulating the molecular weight profiles, including breadth, asymmetry (skewness) and modal nature (mono-, bi-, and multimodal), of a variety of different polyolefins is reported. It involves temporal control over two- and three-state living coordinative chain transfer polymerization (LCCTP) of olefins in a programmable way. By changing the identity of the R' groups of the chain transfer agent, ER'n , with time, different populations of chains within a bi- or multimodal polyolefin product can be selectively tagged with different end-groups. By changing the nature of the main-group metal of the CTA, programmed manipulation of the relative magnitudes of the dispersities of the different maxima that make up the final MWD profile can be achieved. This strategy can be implemented with existing LCCTP materials and conventional reactor methods to provide access to scalable and practical quantities of an unlimited array of new polyolefin materials.

Temporal Control over Two‐ and Three‐State Living Coordinative Chain Transfer Polymerization for Modulating the Molecular Weight Distribution Profile of Polyolefins

AbstractA highly versatile new strategy for manipulating the molecular weight profiles, including breadth, asymmetry (skewness) and modal nature (mono‐, bi‐, and multimodal), of a variety of different polyolefins is reported. It involves temporal control over two‐ and three‐state living coordinative chain transfer polymerization (LCCTP) of olefins in a programmable way. By changing the identity of the R′ groups of the chain transfer agent, ER′n, with time, different populations of chains within a bi‐ or multimodal polyolefin product can be selectively tagged with different end‐groups. By changing the nature of the main‐group metal of the CTA, programmed manipulation of the relative magnitudes of the dispersities of the different maxima that make up the final MWD profile can be achieved. This strategy can be implemented with existing LCCTP materials and conventional reactor methods to provide access to scalable and practical quantities of an unlimited array of new polyolefin materials.

Phenyl-Terminated Polyolefins via Living Coordinative Chain Transfer Polymerization with ZnPh2 as a Chain Transfer Agent

Phenyl-Terminated Polyolefins via Living Coordinative Chain Transfer Polymerization with ZnPh₂ as a Chain Transfer Agent

Modeling of Isoprene Solution Coordinative Chain Transfer Polymerization

AbstractThe present manuscript investigates the solution coordinative chain transfer polymerization (CCTP) of isoprene initiated by the ternary Ziegler‐Natta catalyst system composed by neodymium versatate (), diisobutylaluminum (DIBAH), and dimethyldichlorosilane. A kinetic mechanism is proposed and the kinetic parameters are estimated to allow the appropriate description of dynamic trajectories of average molecular weights and isoprene conversions obtained in solution CCTP polymerizations for the first time. A data reconciliation strategy is applied to evaluate the amount of DIBAH used as a chain transfer agent, as this very active compound can be consumed by undesired side reactions. Additionally, the impacts of key operation variables on the control of the average molecular weights and monomer conversion are evaluated to elucidate the living nature of the polymerization. As observed experimentally, the temperature effect on the course of the polymerization is not so pronounced as the effect of , isoprene, and DIBAH initial concentrations. The kinetic mechanism is described better and kinetic constants are estimated more precisely when the dynamic trajectories of average molecular weights are fitted during the whole batch. In this case, the proposed model is able to predict well the experimental trajectories of average molecular weights of the produced polymer and monomer conversion.

Polymerization via Insertion of Ethylene into Al-C bond under Mild Conditions: Mechanistic Studies on the Promotion Exerted by a Catalytic Amount of Cationic Gadolinium Metallocene.

The cationic gadolinium metallocene [(C5 Me5 )2 Gd][B(C6 F5 )4 ], when combined with an excess amount of Al(i Bu)3 , efficiently produces polyethylene at 80 °C under 0.8 MPa pressure of ethylene. After quenching, the resulting polyethylene has ethyl group at one end and isobutyl group at the other terminal. Because no Gd-alkyl species appears to be involved, a mechanism with conventional coordinative chain transfer polymerization (CCTP) is not feasible. Density functional theory (DFT) analyses indicate a novel mechanism in which the cationic Gd plays a crucial role by coordinating ethylene and assists the insertion of the coordinated ethylene into Al-C bond.

Mechanistic study on the metallocene-based tandem catalytic coordinative chain transfer polymerization for the synthesis of highly branched polyolefins

Creation and control of long-chain branches (LCBs) in coordination polymerization of olefins is an enduring focus of research in both academia and industry. We have recently introduced a tandem catalytic coordinative chain transfer polymerization reaction where upon the concerted function of the polymerization catalyst, the chain transfer agent (CTA), and the displacement catalyst, a highly branched microstructure can be formed. Here we introduce a new tandem catalytic system using Et(Ind)2ZrCl2 as the polymerization catalyst. Despite the optimal reaction temperature for the cooperative function of catalyst components is lower than the ideal temperature for the productivity of the metallocene catalyst, the formation of branches is evident from the decrease and broadening of melting peaks and deviation of rheological properties from characteristic behavior of linear chains in cole–cole plots. Surprisingly, the introduction of the displacement catalyst in CCTP of 1-hexene resulted in low yields and too short polymer chains. Accordingly, we elaborate on the mechanism of this reaction, specifically, we show how the optimal conditions for the (BiPy)2FeEt2 displacement catalyst depend on the monomer type. Namely, the presence of a β–agostic interaction in the bimetallic intermediate formed by the CTA and the displacement catalyst alters the structure of the latter when monomers longer than ethylene are present. This report suggests that our proposed method for the synthesis of branched polyolefins has a great potential for being used in the currently available industrial plants that employ classic metallocene catalysts.

Optical Purity as a Programmable Variable for Controlling Polyolefin Tacticity in Living Coordinative Chain Transfer Polymerization: Application to the Stereomodulated LCCTP of α,ω-Nonconjugated Dienes

Two-state, stereomodulated living coordinative chain transfer polymerization (LCCTP) of 1,6-heptadiene has been achieved to produce a series of cis-poly(methylene-1,3-cyclohexane) (cis-PMCH) with stereochemical microstructures that vary between two limiting forms as a function of the optical purity of the chiral C1-symmetric hafnium preinitiator 1 when activated by the borate co-initiator B1 in the presence of a fixed excess amount of ZnEt2. Optical purity as a programmable variable was demonstrated by premixing the pure homochiral (SC,SHf) and (RC,RHf) enantiomers of 1 in different ratios prior to activation. In contrast, the LCCTP of 1,5-hexadiene using a “racemic” mixture of 1 to produce cis/trans-poly(methylene-1,3-cyclopentane) (cis/trans-PMCP) was less successful due to the loss of stereocontrol for insertion under chain transfer conditions that arises with site epimerization at the transition metal center. A correlation is proposed between the diastereoselectivity and efficiency for the cyclization step in propagation and the magnitude of site epimerization due to reversible chain transfer. These results serve to validate the strategy of using the optical purity of an initiator as a programmable parameter for controlling polyolefin tacticity as well as to better establish the criteria that are required for achieving successful stereomodulated LCCTP for the production of next generation polyolefin materials.

Polyolefin chain shuttling at ansa-metallocene catalysts: legend and reality

Several papers have claimed the amenability for binary metallocene systems to undergo coordinative chain transfer polymerization (CCTP) to produce stereoblock isotactic/syndiotactic polypropylene materials. In this work, we explored through high throughput experimentation (HTE) tools and methods the propensity of the isotactic-selective rac-Me2Si(2-Me-4-Ph-1-Ind)2ZrCl2 (2) catalyst to mediate propene CCTP, individually or in tandem with the syndiotactic-selective ansa-zirconocene Ph2C(Cp)(2,7-di-tBu-9-Flu)ZrCl2 (3), using ZnEt2 and methylalumoxane (MAO) as chain shuttling agents. The results demonstrated that 2 is not prone to propene CCTP, and therefore does not yield stereoblock PP materials when used in racemic form or in tandem with other metallocenes. An unambiguous method to demonstrate the occurrence of CCTP in isotactic propene polymerization, based on the microstructural characterization of the sample by 13CNMR spectroscopy, is also proposed.