Polymeric Complexes Research Articles

Re-use of polyamide-12 in powder bed fusion and its effect on process-relevant powder characteristics and final part properties

Powder bed fusion (PBF) is an additive manufacturing technique capable of fabricating highly complex, individualised, and lightweight polymer components. However, to maximise the potential of PBF, in terms of both economic efficiency and environmental sustainability, a successful powder re-use strategy is essential. During a build, ageing and degradation processes affect the re-usability of un-sintered powder, so used powder is usually refreshed with virgin material before re-use. This study considers the effectiveness of using a 70:30 refresh ratio in a specific PBF technique: laser sintering (LS). Across a total of seven printing cycles, polyamide-12 (PA-12) powder refreshed with 30 % virgin material after each build, revealed a 4.5 °C increase in melting temperature. There was also a 20 % reduction in particle flowability, which may be related to the presence of fine satellite particles and considerable particle cracking. This deterioration in powder quality resulted in a 5.8 % increase in total part porosity, and an 11 % reduction in the ultimate tensile strength of fabricated parts, over the seven build cycles. A Pearson correlation test indicated that the reduction in powder flowability was the most significant (p-value of 0.005) cause for the loss of part strength; emphasising that the revolution powder analyser could be a useful complimentary technique for determining the quality of used powder within laser sintering. Nonetheless, compared to previous studies which re-used 100 % aged PA-12 powder, without refreshing with any virgin material, the observed reduction in part strength is relatively modest. This suggests that a 70:30 refresh ratio offers a good compromise between maintaining part performance, particularly for non-critical applications, without having to add an unnecessary amount of virgin powder. Therefore, this study reveals the relationship between the deterioration of powder properties and reductions in part strength; yet highlights the benefits of operating with a 70:30 refresh ratio when re-using PA-12 powder across multiple build cycles.

Adaptable 2,5-bis((1,2,3-triazol-4-yl)methoxy)pyrazine ligands for the simple self-assembly of homoleptic 1D coordination polymers

This work presents a class of bis-tridentate 2,5-bis((1,2,3-triazol-4-yl)methoxy)pyrazine tzopz ligands, which coordinate to 3d M2+ ions to consistently assemble homoleptic 1D coordination polymers.

Hydrogen bonded polymer complex thin films for highly stretchable gas barriers

Highly flexible buffer-cured hydrogen bonded polymer complex coating demonstrates high oxygen barrier up to 50% strain.

Deciphering polymer degradation chemistry via integrating new database construction into suspect screening analysis.

Water-soluble synthetic polymers and their environmental degradation products are overlooked but important industrial pollutants in wastewater. However, the detection of degradation products is limited to bulk solution chemistry and molecular-level analysis remains unreachable. In this work, we assessed the feasibility of current suspect screening and nontarget workflow using liquid chromatography-high resolution mass spectrometry (LC-HRMS) to elucidate molecular level information about polyacrylamide (PAM) and its degraded products by free radicals. Radical chain scission of PAM (10 kDa) using heat-activated persulfate was conducted to simulate hydraulic fracturing conditions in the deep subsurface. We found that the current workflows in the commercial software generated predicted formulae with low accuracy, due to limited capability of peak picking and formula prediction for high mass and charge features. By modeling literature-reported degradation pathways, we constructed a degradation product database of over 463 000 unique formulae, which improved the accuracy of the predicted formula. For the matched features, the ratio of aldehyde/ketone terminating molecule abundance was found to increase over 24 h degradation time, suggesting increasing content of aldehydes by radical-induced oxidative chain scission of PAM. This is contradictory to previously proposed ratios of carbon-centered radical position on polymer backbone initiated by hydroxyl radicals. Using in silico fragmentation of MS1 features, we identified 11 structures with confidence levels 2b and 3 using their MS2 information. This is the first attempt to resolve complex polymer degradation chemistry using HRMS that can advance our ability to detect water-soluble polymer pollutants and their transformation products in environmental samples.

Truxinates and truxillates: building blocks for architecturally complex polymers and advanced materials.

Significant advancements in the syntheses of cyclobutane containing small molecules and polymers are described in the last 15 years. Small molecule cyclobutanes are under investigation for their diverse pharmacological activities, while polymers with cyclobutane backbones are emerging as novel mechanophores, stress-responsive materials, and sustainable plastics. Within these chemistries, [2 + 2] photocycloadditions to yield truxinates and truxillates are highly efficient offering a versatile strategy to access complex scaffolds. This article provides a comprehensive review on the synthetic methodologies, properties, and applications of polymer truxinates and truxillates, providing the background necessary to understand current developments and envision future applications. Additionally, we highlight the links between the development, discoveries, and synthetic methodologies of small molecules and cyclobutane polymers. We emphasize structure property relationships and discuss methods to control composition and structure for desired applications. We begin with a discussion of synthetic techniques for small molecule and polymer cyclobutanes followed by their greater applications, including pharmacological and material properties with examples including sustainable plastics and stimuli-responsive systems.

Mechanically induced cationic reversible addition-fragmentation chain transfer polymerization of vinyl ethers.

Mechanoredox catalysis has emerged as a sustainable approach for organic transformations. Mechanically controlled polymerization that uses mechanoredox catalysts enables synthesis of complex polymers and mechanoresponsive materials with diverse applications. Despite its potential, the focus has predominantly been on free radical polymerization and acrylate monomers. The mechanochemical synthesis of poly(vinyl ether)s (PVEs) poses a significant challenge in the field. Herein, we report an efficient mechanically induced cationic reversible addition-fragmentation chain transfer (mechano-cRAFT) polymerization using 2D MoS2 as a mechanoredox catalyst, where free radical intermediates can be further oxidized to cations to promote cationic polymerization of vinyl ethers. This mechano-cRAFT polymerization can be conducted in air and with minimal organic solvent, resulting in quantitative monomer conversion. This strategy is applicable to a range of vinyl ether monomers, yielding polymers with controlled molecular weight and narrow dispersity. We also performed trapping experiments to investigate the piezoelectrically mediated redox process, and further validated the mechanism through density functional theory (DFT) calculations.

Enhancing the dewatering of oil sands mature fine tailings by coagulation-flocculation and pressure filtration with tannic acid-mediated polymeric complex network

This study presents a new method to improve the dewatering efficiency of oil sands mature fine tailings (MFT) by pressure filtration using a tannic acid-mediated polymeric complex network as a flocculant. It was found that the prior addition of tannic acid ahead of poly(ethylene oxide) and ferric chloride significantly increased the vacuum filtration rate by improving the permeability of the filter cake and reducing its specific resistance to filtration. The beneficial role of tannic acid was investigated by slurry shear stress, sedimentation, floc morphology and size distribution measurements, and UV–Vis and FTIR spectroscopic characterization. Results indicated that tannic acid acted as a crosslinker to complex with both poly(ethylene oxide) and ferric chloride to develop a tri-component polymeric network. Within the network, numerous hydrogen bonds and coordination bonds enabled a sufficient crosslinking density, resulting in higher floc strength and compression resistance. Flocs generated by the tannic acid-mediated polymeric network were more rigid with an expanded structure, allowing drainage channels to remain open in the filter cake for better permeability. Scale-up experiments on a Millipore pressure filtration unit verified the beneficial role of tannic acid in filtering the mature fine tailings, achieving a much higher net water release rate and cake solid content.

Solubility Prediction and Dissolution Mechanism Analysis of Etodolac in Complex Polymer Solutions Based on Thermodynamic and Interfacial Mass Transfer Models

Solubility Prediction and Dissolution Mechanism Analysis of Etodolac in Complex Polymer Solutions Based on Thermodynamic and Interfacial Mass Transfer Models

A green pathway for lignin valorization: Enzymatic lignin depolymerization in biocompatible ionic liquids and deep eutectic solvents

Lignin depolymerization, which enables the breakdown of a complex and heterogeneous aromatic polymer into relatively uniform derivatives, serves as a critical process in valorization of lignin. Enzymatic lignin depolymerization has become a promising biological strategy to overcome the heterogeneity of lignin, due to its mild reaction conditions and high specificity. However, the low solubility of lignin compounds in aqueous environments prevents efficient lignin depolymerization by lignin-degrading enzymes. The employment of biocompatible ionic liquids (ILs) and deep eutectic solvents (DESs) in lignin fractionation has created a promising pathway to enzymatically depolymerize lignin within these green solvents to increase lignin solubility. In this review, recent research progress on enzymatic lignin depolymerization, particularly in a consolidated process involving ILs/DESs is summarized. In addition, the interactions between lignin-degrading enzymes and solvent systems are explored, and potential protein engineering methodology to improve the performance of lignin-degrading enzymes is discussed. Consolidation of enzymatic lignin depolymerization and biocompatible ILs/DESs paves a sustainable, efficient, and synergistic way to convert lignin into value-added products.

Using Mechanochemistry to Activate Commodity Plastics as Initiators for Radical Chain Reactions of Small Organic Molecules.

Radical initiators such as azo compounds and organic peroxides have been widely used to facilitate numerous transformations of free radicals, which enable the efficient synthesis of structurally complex molecules, natural products, polymers, and functional materials. However, these high-energy reagents are potentially explosive and thus often require special precautions or delicate operating conditions. We postulated that a more convenient and safer alternative for radical chain initiation could be developed by mechanical activation of thermodynamically stable covalent bonds. Here, we show that commodity plastics such as polyethylene and poly(vinyl acetate) are capable of acting as efficient initiators for radical chain reactions under solvent-free mechanochemical conditions. In this approach, polymeric mechanoradicals, which are generated by homolytic cleavage of the polymer chains in response to the applied mechanical energy provided by ball milling, react with tris(trimethylsilyl)silane to initiate radical chain dehalogenation of organic halides. Preliminary calculations support our proposed force-induced radical chain mechanism.

(Invited) Stable Layered Oxyhalide Photocatalysts for Visible-Light-Induced Water Splitting

Water splitting using photocatalysts has attracted considerable attention for producing H2 as a clean energy carrier, while the effective utilization of visible light is imperative to achieve the desired efficiency for practical applications. Recently, mixed-anion compounds such as oxynitrides have been intensively studied as promising candidates since one can expect that higher energy p orbitals of non-oxide anions (e.g., N-2p) elevate their VBM values. Unfortunately, most of them are subject to facile self-oxidation by photogenerated holes, while highly dispersed cocatalyst particles certainly improve the stability of some oxynitrides.Recently, we have revealed that some layered perovskite oxyhalides fulfil the necessary conditions for visible-light-induced water splitting due to their unique VBMs. For example, Bi4NbO8Cl belongs to the n = 1 members of the Sillén–Aurivillius perovskite family [(Bi2O2)2X]3+[A n -1BnO3n+1]3, which is composed of fluorite [Bi2O2], perovskite [NbO4], and halogen [Cl] layers as depicted in Figure 1. DFT calculations show that the VBM mainly consists of O-2p orbitals instead of Cl-3p, but its position determined by electrochemical measurement is much more negative (ca. 2.2 V vs. SHE) than those of conventional metal oxides (ca. 3.0 V). The significantly elevated VBMs of Bi4NbO8Cl can be understood by the strong hybridization between electron-filled Bi-6s and O-2p with the help of empty Bi-6p orbitals. In addition, Madelung site potential analysis for Bi4NbO8Cl indicated that the oxygen sites in the fluorite layer were electrostatically destabilized, which also certainly contributed to the elevation of the VBM that mainly consists of O-2p. Consequently, Bi4NbO8Cl possesses both a narrow band gap (2.4 eV) for visible light absorption up to ca. 500 nm and a more negative CBM (ca.–0.2 V vs. SHE) than the water reduction potential, which were testified by the substantial generation of H2 or O2 in the presence of an electron donor or acceptor, respectively. The substantially high durability against self-oxidative deactivation was also confirmed by the long-term water splitting in a Z-scheme system in which Bi4NbO8Cl was employed as the OEP. Since O– anions are known to be relatively stable, photogenerated holes populated at the O-2p orbitals will not lead to self-oxidative decomposition but rather to the oxidation of water.More oxyhalides with various perovskite layers (n) have been explored. However, reports on the synthesis of multiple-layered (n ≥ 2) perovskites were limited, probably due to the severe conditions required for their synthesis in the conventional solid state reaction. To solve this problem, a new two-step synthesis method including polymerized complex synthesis and a “bricklaying” synthesis were developed; providing a wide variety of new oxyhalides applicable to visible-light-induced water splitting. We also demonstrate that a oxyiodides such as Ba2Bi3Nb2O11I not only has access to a wider range of visible light than its chloride and bromide counterparts, but also exhibit much higher activity due to longer lifetime of photogenerated carriers.These studies on new oxyhalide materials provide new strategies for developing stable photocatalysts for visible-light-induced water splitting by manipulating the interaction between the s orbitals of post-transition metals (e.g., Bi-6s) and O-2p orbitals in the specific crystal structure.

Supercritical CO2 Assisted Ni-P Electroless Plating of PET Components with Complex 3D Structures

There is an increasing demand of methodologies to metallize complex polymer materials for application in electronics such as wearable devices and robotic products. In various metallization methods, electroless plating is a powerful and promising approach to meet this demand. The present conventional electroless plating requires pretreatment steps to deposit catalyst onto surfaces of polymer materials, which results in damages to their surfaces and also deformation of their shape because of the usage of strong acidic solvents. Furthermore, the adhesion strength between the polymer material and the metal layer is insufficient. To overcome these problems, a catalyzation step using supercritical carbon dioxide (sc-CO2) as the solvent is proposed.[1] The sc-CO2-assisted catalyzation enables a deep impregnation of catalysts into the polymer material without the pretreatment step, and this enhances the adhesive properties of the deposited metal on the polymer. By the sc-CO2-assisted catalyzation, electroless Ni-P plating of polyethylene terephthalate (PET) is realized. [1] Metallization of polymer materials with complex 3D structures is a more attractive topic, but it is widely accepted to be more difficult than film structures. Also, application the electroless plating via sc-CO2-asssited catalyzation to 3D-structured polymer materials remains unexplored. In this presentation, we report Ni-P plating of PET samples having complex 3D structures by the sc-CO2-assisited catalyzation process.A PET based material with a concavo-convex structure was designed and fabricated by the processing machine as shown in Figs. 1(a)–(b). Sc-CO2-assisted catalyzation process was performed in a high pressure reactor[1] containing palladium (II) hexafluoroacetylacetonate (Pd(C5HF6O2)2) as the palladium catalyst source at 70 °C under 15 MPa for 2 h. After the catalyzation process, the reactor was cooled to room temperature while maintaining the pressure in the reactor, and then the pressure in the reactor was reduced to atmospheric pressure. The collected PET sample from the reactor was kept under ambient atmosphere for two weeks, and then it was subjected to electroless Ni-P plating at 70 ℃ for 10 min.Fig. 1(c) shows the PET sample obtained after the sc-CO2-assisted catalyzation process followed by the post-treatment process. The volume of the catalyzed PET sample was scarcely changed. On the other hand, the post-treatment processes performed under the different conditions were found to cause undesired swelling and white turbidity of the PET sample, presumably because of microbubbles derived from residual CO2 in the PET. Fig. 1(d) shows an image of Ni-P successfully metallized on the PET surface. The electrical resistance of the Ni-P/PET material was 8.7 Ω, which is acceptable for electronic device applications. From these results, we concluded that sc-CO2-assisted catalyzation is applicable to metallization of PET materials with complex 3D structures. Reference [1] P.-W. Cheng, C.-Y. Chen, T. Ichibayashi, T.-F.M. Chang, M. Sone, S. Nishimura, J. Supercrit. Fluids 180 (2022) 105455. Figure 1

1D-photosensitized lanthanide polymers with flexible 4, 4′-bipyridyl linker

Three new ternary lanthanide complexes, [Ln(fod)3(4,4′-bpy)]n (Ln = Nd, Sm and Tb) were synthesized using asymmetric fluorinated β-diketone, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, as first sensitizer and 4, 4′-bipyridyl, the linker. The structural characterizations were carried out through various techniques viz., 1H NMR, FT-IR, single crystal X-ray diffraction (SC-XRD) and thermal analysis. Single crystal X-ray diffraction (SC-XRD) analysis demonstrates a 1D-polymeric chain structure of [Nd(fod)3(4,4′-bpy)]n in which Nd (III) ions are octa-coordinate with distorted square antiprismatic geometry. The structure of samarium and terbium complexes were optimized by the sparkle PM7 model using MOPAC implemented in LUMPAC and found to be distorted triangular dodecahedron The thermal studies shows that the complexes are thermally stable and acquire volatility without decomposition. The 1H NMR of these complexes are similar. The protons of 4, 4ʹ-bpy are largely shifted upfield in the Tb complex followed by Nd and Sm. The detailed photoluminescence and decay curves of these polymeric complexes have been discussed in solution and solid state. The emission spectra obtained for all the complexes display their characteristic emission peaks. The terbium complex shows pure green luminescence and exhibits a longer lifetime of 406 µs. The [Sm(fod)3(4,4′-bpy)]n displays color tuning during interphase and also with a change in excitation wavelength from turquoise to pure yellow via green. All the synthesized complexes exhibiting remarkable photophysical properties ensures their importance in various fields.

Specifics of Pharmacokinetics and Biodistribution of 5-Fluorouracil Polymeric Complex.

Monomeric methacrylic acid was used to synthesize polymers; 2-phenylpropane-2-ilbenzodithioate was used for the synthesis of poly(methacrylic acid). To study the molecular-weight characteristics of poly(methacrylic acid) by gel permeation chromatography, an experimental neoplasm model was obtained by grafting PC-1 cancer cells. Blood samples were drawn from the tail vein at different points in time. The rats were sacrificed via decapitation after drawing the last pharmacokinetic blood sample. To study the biodistribution, internal organs were isolated and analyzed. The measurements were carried out by high-performance liquid chromatography. Our results demonstrate that incorporation in a polymeric complex changes the pharmacokinetics and biodistribution profile of 5-FU. The polymeric complex was shown to accumulate to a higher level in the lung and spleen. The results obtained are the basis for further studies to verify the efficacy of the 5-Fluorouracil polymeric complex.

Novel bioactive copper and nickel polymeric complexes: Synthesis, characterization, antimicrobial activity, and DFT calculations

AbstractPolymeric complexes, especially metal‐containing polymers, possess aggregated medical applications, especially as antibacterial and antifungal agents. This work describes a facile procedure for producing a series of novel copper and nickel complexes of poly(2‐hydroxyphenyl methacrylamide) and poly(2‐carboxyphenyl methacrylamide). The polymeric ligands were synthesized through a multistep procedure. Firstly, 4‐formylphenyl methacrylate was constructed by acylating 4‐hydroxybenzaldehyde with methacryloyl chloride. Then, polymerization of the as‐prepared monomer to obtain poly(4‐formylphenyl methacrylate) using benzoyl peroxide as an initiator. Thirdly, the polymeric ligands PL1 and PL2 were achieved via exchange reactions between poly(4‐formylphenyl methacrylate) and o‐aminophenol and anthranilic acid, respectively. Consequently, the two ligands were reacted with copper and nickel acetates to afford four target complexes (Cu‐PL1, Ni‐PL1, Cu‐PL2, and Ni‐PL2). By FT‐IR, 1HNMR, UV‐visible, and TGA analyses, the structures of PL1, PL2, and their complexes were investigated. Furthermore, the geometries of PL1, PL2, and their complexes were reported through a molecular modeling to investigate some interesting parameters such as the bond length, bond angle, charge on the atoms, the HOMO and LUMO using the Material Studio program. The calculation results illustrated that octahedral geometries are proposed for the synthesized metal complexes. The reported antimicrobial efficiency showed a strong potency for most synthesized compounds against the selected microbes, especially compounds Cu‐PL1 and Cu‐PL2 which are more effective than the standard against Candida albicans.

45 Years of Polymer HPLC: A Short Review

AbstractUntil the end of the 70s of the last century, the major tool for fractionating complex polymers regarding molecular size is gel permeation chromatography (GPC) (more accurately size exclusion chromatography, SEC). A milestone in fractionating polymers with regard to chemical composition is achieved when it is shown that random copolymers can be separated according to copolymer composition using solvent gradient HPLC. Another important step toward selective fractionation is taken when liquid chromatography at the critical point of adsorption is introduced as an efficient way to separate functional polymers with regard to their functionality type distribution. Another milestone is the discovery that temperature gradients can also be used for the selective separation of complex polymers with regard to composition. The combination of different LC methods in comprehensive 2D HPLC setups is another milestone. As of today, a toolbox of HPLC methods is in place that enables the fractionation of complex polymers according to all molecular parameters including tacticity and branching. Here, an overview on the different techniques and some major applications is presented. The most important developments in the field are discussed, and different techniques, experimental protocols, and applications are highlighted. In conclusion, challenges for future developments are outlined.

Investigating the Role of Odorant-Polymer Interactions in the Aroma Perception of Red Wine: A Density Functional Theory-Based Approach.

The aroma of red wine results from the intricate interplay between aroma compounds (odorants) and complex polymers generated during fermentation. This study combines density functional theory (DFT), human sensory experiments, and nuclear magnetic resonance to investigate the impact of odorant-polymer interactions on wine aroma. Molecular aggregation patterns of odorants with polymer segments are identified, indicating the crucial role of intermolecular noncovalent interactions, such as hydrogen bonds and van der Waals interactions, in stabilizing odorant-polymer conformations. Certain odorants, including 3-isobutyl-2-methoxypyrazine and cis-whisky lactone, exhibit high binding affinity to specific polymer segments, such as (+)-catechin and p-coumaric acid, resulting in substantial changes in the perceived aroma. Their strong binding affinities correlate with changes in sensory experiments for binary mixtures. The results provide insights into the molecular mechanisms of odorant-polymer interactions in red wine with the potential of DFT calculations as a tool for predicting and tailoring red wine aroma.

Study of structural, electrical, and electrochemical properties of Sr3-xPrxFe1.8Co0.2O7-δ cathode for IT-SOFCs

Developing new cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs) is still challenging. In this study, co-doped Sr3Fe2O7-δ Ruddlesden-Popper (R-P) (Sr3-xPrxFe1.8Co0.2O7-δ x = (0–0.3)) cathode is synthesized by the polymer complex technique as a cathode for IT-SOFCs. The synthesized powders show a desired tetragonal structure of Sr3-xPrxFe1.8Co0.2O7-δ with an I4/mmm space group. The effect of Pr and Co on the physical, thermal, electrical, and electrochemical properties of the cathodes is investigated. The results reveal that Pr/Co co-doping improves electrochemical properties while increasing the electrical resistivity and average thermal expansion coefficients (TECs). To evaluate the long-term thermal stability of the cathode, they are heated at 800 °C for 100 h in the air, and no contaminant is found. In the optimal amount of Pr and Co (Sr2.7Pr0.3Fe1.8Co0.2O7-δ), area-specific resistance (ASR) of 0.058 Ω.cm2 and maximum output power density of 745 mW/cm2 are obtained at 800 °C. Strong oxygen-reducing reaction (ORR) activity and long-term thermal stability make Sr2.7Pr0.3Fe1.8Co0.2O7-δ an appropriate alternative cathode material for IT-SOFC.

Polyvinyl alcohol stabilized ZnS nanoaggregates using organosulfur source for photocatalytic disintegration of methyl orange dye

ZnS nanoaggregates surface-passivated by a hydroxyl-based polymer matrix, polyvinyl alcohol (PVA), have been synthesized using a wet chemical method and an organosulphur precursor. The nanocomposite was characterized by XRD, SEM, and FTIR. XRD patterns revealed wurtzite structure. FTIR spectrum confirmed the interaction of hydroxyl group of PVA with the ZnS. We proposed a probable pathway for the precipitation of zinc sulfide by alkaline hydrolysis of complex formed from (NH2)2CS and Zn2+-polymer complex. The optical properties were monitored using UV–Vis spectroscopy and photoluminescence (PL) spectroscopy. Quantum confinement of electrons is confirmed by increase in the optical band gap and determined to be 3.91 eV. The photocatalytic activity of the ZnS/PVA nanoaggregates particles was examined using methyl orange (MO). After 3 h of illumination, the photocatalytic degradation rate of methyl orange (MO) is about 94.20 %.

Marriage of Organic and Grubbs Catalysts for Tandem Synthesis of Bottlebrush Polyesters.

Bottlebrush polymers (BBPs) have gained wide attention for their special characters, such as rigid main/side chains, stemming from the exceedingly high graft density. This study aims to provide a simple synthetic approach to BBPs with polyester side chains by merging ring-opening alternating copolymerization (ROAP) and ring-opening metathesis polymerization (ROMP). A simple phosphazene base (tBuP1) is employed for the ROAP of phthalic anhydride and epoxide, after which Grubbs third-generation catalyst (G3) is added to in situ switch on ROMP of the macromonomer, i.e., norbornenyl-ended alternating polyester. The compatibility of tBuP1 with G3 and well-controlled ROMP is evidenced by DOSY-NMR of mixed catalysts, characterization of BBPs, and side-chain degradation. The method can also be extended to BBPs with one-step synthesized block copolyesters side chains. These results highlight the strength of the non-nucleophilic organobase catalyst for convenient construction of complex (degradable) polymers with compositional diversity.