Ring-opening Metathesis Polymerization Research Articles

Synthesis and Application of Amphiphilic Block Copolymer

The amphiphilic di- and tri-block copolymer is widely used to solve many seemingly intractable problems in our lives. They have the potential to help curing the cancel and some of them already in clinical application. Besides, it can work as a stabilizer of dispersions to disperse insoluble substance in certain solvents to make the substance work better. After decades of scientists’ exploring, the living polymerization have been frequently used in living polymerization. In addition, the simple and efficient methods laying the foundation of the various application of amphiphilic di/tri-block copolymer. In this research, the living radical polymerization, such as reversible deactivation radical polymerization (RDRP) and ring-opening metathesis polymerization (ROMP), are mentioned. And the living anionic polymerization is the main approach synthesize a diverse of different block copolymers, where the reaction mechanism is further discussed in this research. After analyzing the properties of amphiphilic di- and tri-block copolymer to find why it can be used for drug delivery and as a stabilizer of dispersions, some applications for amphiphilic di- and tri-block copolymers will be introduced. With such advanced synthesis methods, however, the application of amphiphilic block copolymer is mainly in drug delivery. As a result, there might be some potential applications for amphiphilic di- and tri-block copolymer.

Alternating Ring-Opening Metathesis Polymerization Promoted by Ruthenium Catalysts Bearing Unsymmetrical NHC Ligands

In this paper, Grubbs- and Hoveyda–Grubbs-type olefin metathesis catalysts featuring N-cyclopentyl/N’-mesityl backbone-substituted N-heterocyclic carbene (NHC) ligands were synthesized. Their propensity to promote the alternating ring-opening metathesis copolymerization (ROMP) of norbornene (NBE) with cyclooctene (COE) or cyclopentene (CPE) was evaluated and compared to that shown by analogous N-cyclohexyl complexes. High degrees of chemoselectivity were achieved in both copolymerizations. The presence of the N-cyclopentyl substituent allowed for the achievement of up to 98% and 97% of alternating diads for NBE-COE and NBE-CPE copolymers, respectively, at low comonomer ratios. Density functional theory (DFT) studies showed that both the sterical and electronic effects of NHC ligands influence catalyst selectivity.

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers.

The growing consumption of synthetic polymers and the accumulation of polymer waste have led to a pressing need for new routes to sustainable materials. Achieving a closed-loop polymer economy via chemical recycling to monomer (CRM) is one such promising route. Our group recently reported a new CRM system based on polymers prepared by ring-opening metathesis polymerization (ROMP) of trans-cyclobutane fused cyclooctene (tCBCO) monomers. This system offers several key advantages, including the ease of polymerization at ambient temperatures, quantitative depolymerization to monomers under mild conditions, and a broad range of functionalities and thermomechanical properties. Here, we outline detailed protocols for the preparation of tCBCO-based monomers and their corresponding polymers, including the preparation of elastic polymer networks and compression molding of linear thermoplastic polymers. We also outline the preparation of high ring strain E-alkene tCBCO monomers and their living polymerization. Finally, the procedures for the depolymerization of linear polymers and polymer networks are also demonstrated.

Chiral Polymers from Norbornenes Based on Renewable Chemical Feedstocks.

Optically active polymers are of great interest as materials for dense enantioselective membranes, as well as chiral stationary phases for gas and liquid chromatography. Combining the versatility of norbornene chemistry and the advantages of chiral natural terpenes in one molecule will open up a facile route toward the synthesis of diverse optically active polymers. Herein, we prepared a set of new chiral monomers from cis-5-norbornene-2,3-dicarboxylic anhydride and chiral alcohols of various natures. Alcohols based on cyclic terpenes ((-)-menthol, (-)-borneol and pinanol), as well as commercially available alcohols (S-(-)-2-methylbutanol-1, S-(+)-3-octanol), were used. All the synthesized monomers were successfully involved in ring-opening metathesis polymerization, affording polymers in high yields (up to 96%) and with molecular weights in the range of 1.9 × 105-5.8 × 105 (Mw). The properties of the metathesis polymers obtained were studied by TGA and DSC analysis, WAXD, and circular dichroism spectroscopy. The polymers exhibited high thermal stability and good film-forming properties. Glass transition temperatures for the prepared polymers varied from -30 °C to +139 °C and, therefore, the state of the polymers changed from rubbery to glassy. The prepared polymers represent a new attractive platform of chiral polymeric materials for enantioselective membrane separation and chiral stationary phases for chromatography.

Cyclophanediene and Cyclophanetriene‐Based Conjugated Polymers

AbstractPoly(p‐phenylene vinylene)s (PPVs) and poly(arylene vinylene)s are key materials for a variety of applications ranging from organic light emitting diodes to fluorescent optical probes. Their syntheses, however, have been hampered by non‐living or step‐growth polymerization techniques. The development of functional‐group tolerant olefin metathesis catalysts has enabled the use of living ring‐opening metathesis polymerization (ROMP) of cyclophane monomers yielding PPVs and poly(p‐phenylene‐co‐arylene vinylene)s in a living manner. Low dispersity and soluble PPVs are afforded with control over the number of repeat units with easy incorporation of different end‐groups at their heads or tails. In this review, a comprehensive overview of tetrasubstituted and disubstituted alkyl and alkoxy containing [2.2]paracyclophane‐1,9‐diene, [2.2]metaparacyclophane‐1,9‐diene, [2.2.2]paracyclophane‐1,9,17‐triene, and benzothiadiazole‐[2.2]paracyclophane‐1,9‐diene is provided. The high ring strain of these monomers enables efficient polymerizations with ruthenium initiators. A particular emphasis is on [2.2]paracyclophane‐1,9‐dienes as it is the most investigated class of polymerized cyclophanediene since initially reported 30 years ago. Additionally, applications for soft materials synthesized by ROMP are examined, highlighting easily accessed PPV copolymers and PPV block copolymers that can be phototriggered, as well as PPVs featuring supramolecular recognition units installed at their termini to afford orthogonally self‐assembled architectures.

Stereoselective Ring‐Opening Metathesis Polymerization with Tungsten Sulfido Alkylidene N‐Heterocyclic Carbene Complexes

AbstractA series of cationic tungsten sulfido alkylidene N‐heterocyclic carbene (NHC) complexes (W01 – W09) of the general formula [W(S)(CHCMe3)(X)(NHC)(CMe3CN)+B(ArF)4−] (NHC = 1,3‐dimesitylimidazol‐2‐ylidene, IMes; 1,3‐dimesityl‐4,5‐dichloroimidazol‐2‐ylidene, IMesCl2; 1,3‐bis(2,6‐xdiisopropyl)phenyl)imidazol‐2‐ylidene, IDipp; X = Cl, C6F5O, 2,6‐Ph2‐C6H3; B(ArF)4− = tetrakis(3,5‐bis(trifluoromethyl)phenyl)borate) are used as initiators in the stereoselective ring‐opening metathesis polymerization (ROMP) of (+) 2,3‐endo, exo‐dicarbomethoxynorborn‐5‐ene ((+)DCMNBE, M1). Trans‐isospecifity up to 84% is achieved along with varying percentages of cis‐syndiospecifity. The different extent of trans‐isospecifity is compared to the one of related benchmark cationic molybdenum and tungsten imido and tungsten oxo alkylidene NHC complexes. Mechanistic investigations suggest that the syn‐isomer of a nitrile‐free initiator reacts with M1 presumably in an eneanti fashion to yield a syn‐first insertion product via turnstile rearrangement, which accounts for the predominant trans‐isospecifity of the polymerization. The cis‐syndiotactic sequences are proposed to stem from the competing enesyn addition of M1 to a nitrile‐containing syn‐isomer of the initiator.

Synthesis and Ring-Opening Metathesis Polymerization of o-Dialkoxy Paracyclophanedienes.

The highly strained ortho-diethylhexyloxy [2.2]paracyclophane-1,9-diene (M1) can be synthesized by ring contraction of a dithia[3.3]paracyclophane using a benzyne-induced Stevens rearrangement. This paracyclophanediene undergoes ring-opening metathesis polymerization to give well-defined 2,3-dialkoxyphenylenevinylene polymers with an alternating cis/trans alkene stereochemistry and controllable molecular weight. Fully conjugated block copolymers with electron-rich and electron-deficient phenylene vinylene polymer segments can be prepared by sequential monomer additions. These polymers can be readily isomerized to the all-trans stereochemistry polymer. The optical and electrochemical properties of these polymers were investigated by theory and experiment.

Dihydroxy Polyethylene Additives for Compatibilization and Mechanical Recycling of Polyethylene Terephthalate/Polyethylene Mixed Plastic Waste.

Polymer blend compatibilization is an attractive solution for mechanical recycling of mixed plastic waste because it can result in tough blends. In this work, hydroxy-telechelic polyethylene (HOPEOH) reactive additives were used to compatibilize blends of polyethylene terephthalate (PET) and linear low-density polyethylene (LLDPE). HOPEOH additives were synthesized with molar masses of 1-20 kg/mol by ring-opening metathesis polymerization of cyclooctene followed by catalytic hydrogenation. Melt-compounded blends containing 0.5 wt % HOPEOH displayed reduced dispersed phase LLDPE particle sizes with ductilities comparable to virgin PET and almost seven times greater than neat blends, regardless of additive molar mass. In contrast, analogous blends containing monohydroxy PE additives of comparable molar masses did not result in compatibilization even at 2 wt % loading. The results strongly suggest that both hydroxy ends of HOPEOH undergo transesterification reactions during melt mixing with PET to form predominantly PET-PE-PET triblock copolymers at the interface of the dispersed and matrix phases. We hypothesize that the triblock copolymer compatibilizers localized at the interface form trapped entanglements of the PE midblocks with nearby LLDPE homopolymer chains by a hook-and-clasp mechanism. Finally, HOPEOH compounds were able to efficiently compatibilize blends derived solely from postconsumer PET and PE bottles and film, suggesting their industrial applicability.

Synthetic Route And Application of Photodegradable Polymers

With the accumulating mass of land wastes, designing end-of-life principles for plastic wastes is becoming one of the most debated topics for polymer scientists. A developing family of materials called photodegradable polymers carries great environmental and commercial values. Photodegradable polymers will engage in photolysis under specific wavelengths, resulting in cleavages on the polymer backbone and smaller molecular weights. This research will discuss standard methods of photodegradation, such as Norris I&II, along with common photodegradable polymers and their functionalities. Examples of photodegradable polymers illustrated are polybutadiene, isotactic poly(propylene oxide) (iPPO), polylactide (PLA), and polystyrene. In Particular, this research used polystyrene as an example to explain the common degradation steps of photodegradable polymers. Nevertheless, the synthetic route and plans utilized for those polymers are discussed, shedding light on future possibilities in this field. Promising directions, such as metal-organic polymers with metal-to-metal bonds that can be synthesized through ring-opening metathesis polymerization (ROMP) are touched upon by the end of the research, introducing possible future implications in polymer science.

Practical Route for Catalytic Ring-Opening Metathesis Polymerization.

Norbornene derivatives are typical monomers for ring-opening metathesis polymerization (ROMP) for synthesizing highly functional polymers. However, the lack of catalytic methods, that is, the lack of readily available chain transfer agents (CTAs) for these monomers has been a significant cost limitation when large-scale syntheses are required. Here, we report commercially available styrene and its derivatives as efficient regioselective CTAs for the catalytic synthesis of metathesis polymers requiring up to 1000 times less ruthenium than in classical ROMP experiments. The molecular weight of the synthesized polymers was controlled by the monomer-to-CTA ratio. Low molecular weight ROMP polymers known for their antimicrobial properties were also synthesized on a gram scale in this report. Polymers were characterized by SEC, 1H NMR spectroscopy, and isotopically resolved MALDI-TOF MS. This approach describes a greener, more cost-effective, and eco-friendly methodology for the preparation of metathesis-based materials on the multigram scale.

Polymer Molecular Weight Determination via Fluorescence Lifetime.

Control of polymer molecular weight is critical for tailoring structure-function properties; however, traditional molecular weight characterization techniques have limited ability to determine the molecular weight of polymers in real time without sample removal from the reaction mixture, with spatial resolution, and of insoluble polymers. In this work, a fluorescence lifetime imaging microscopy (FLIM) method was developed that overcomes these limitations. The method is demonstrated with polynorbornene and polydicyclopentadiene, polymers derived from ruthenium-catalyzed ring-opening metathesis polymerization (ROMP). The polymer Mw, ranging from 35 to 570 kg/mol as determined by gel-permeation chromatography, was quantitatively correlated with the fluorescence lifetime. The revealed correlation then enabled time-resolved measurement of Mw during an ongoing ROMP reaction, requiring only 1 s per measurement (of a 45 μm × 45 μm polymer sample area), and provided spatial resolution, resulting in simultaneous characterization of polymer morphology. To provide the fluorescence signal, the initial reaction solutions contained a very low doping of a reactive norbornene monomer labeled with fluorescent boron dipyrromethene (BODIPY), such that 1 in every 107 monomers contained a fluorophore. The resulting FLIM visualization method enables the rapid determination of the molecular weights of growing polymers without removal from the reaction mixture and regardless of polymer solubility.

Norbornene-Substituted Cationic Iridium(III) Complex and Water-Soluble Luminescent Polymers Based on It: Synthesis, Photophysical and Cytotoxic Properties

A norbornene-substituted cationic iridium(III) complex containing 1-phenylisoquinoline cyclometalating ligands and an additional phenylimidazophenanthroline ligand was synthesized. On the base of this complex, water-soluble polymers were obtained by ring-opening metathesis polymerization (ROMP). The resulting polymers showed oxygen-dependent phosphorescence in the orange spectral region and high cytotoxicity against HCT116 cancer cells.

Ring-Opening Metathesis Polymerization for the Synthesis of Terpenoid-Based Pressure-Sensitive Adhesives.

Pressure-sensitive adhesives (PSAs) made from norbornene-functionalized terpenoid-based monomers are reported as a possible alternative to the conventional petrochemically based PSAs. For this, tetrahydrogeranyl, menthyl, and isobornyl norbornenate monomers, with a renewable carbon content up to 72%, are synthesized and copolymerized via ring-opening metathesis polymerization (ROMP) with cyclooctadiene and 5-norbornene-2-carboxylic acid. ROMP enables a much faster and controlled polymerization process in comparison to free radical polymerization techniques when targeting high molecular weights and therefore unlocks a potential to design a unique class of PSA materials. The moduli at bonding and debonding frequencies of the obtained PSAs are plotted in the Chang classification system and are used to predict their adhesive performance. Tack and peel measurements indicate that the terpenoid-based norbornenate formulations show similar adhesive properties in comparison to the previously investigated acrylic counterparts.

Macrochain Transfer Agents for Catalytic Ring-Opening Metathesis Polymerization.

A monosubstituted 1,3-diene derivative attached to a polymer is demonstrated to act as a macrochain transfer agent in catalytic ring-opening metathesis polymerization. PEG- and PLA-based macrochain transfer agents were synthesized in a few steps and were characterized using NMR spectroscopy, size exclusion chromatography (SEC) and matrix-assisted laser desorption/ionization-time-of-flight (MALDI-ToF) mass spectrometry. Poly(l-lactide) based diblock copolymer, poly(ethylene glycol)-based diblock, and triblock (ABA type) copolymers of varied chain lengths were prepared catalytically in a one-pot approach via metathesis polymerization. Block copolymers were characterized by SEC and showed monomodal molecular weight distributions. Moreover, DOSY NMR spectroscopy further proved the block microstructures of the synthesized polymers.

Hydrogen-Bonding Bottlebrush Networks: Self-Healing Materials from Super-Soft to Stiff

The impact of polymer architecture on network dynamics and self-healing is presented using bottlebrushes containing side chains that are end-functionalized with 2-ureido-4[1H]-pyrimidinone (UPy). The synthesis of these materials is straightforward through a three-step process: (1) synthesizing rubbery poly(4-methylcaprolactone) macromonomers (p4MCL–OH) with a norbornene-based initiator, (2) functionalizing the terminal hydroxyl group with UPy–isocyanate (p4MCL–UPy), and (3) statistically copolymerizing p4MCL–OH and p4MCL–UPy via ring-opening metathesis polymerization (ROMP) to form hydrogen-bonding bottlebrushes having a fraction (p) of side chains functionalized with UPy. Attaching UPy to the free end of bottlebrush side chains dilutes the impact of friction from complementary UPy interactions on segmental dynamics, leading to a much weaker dependence of the glass-transition temperature (Tg) on p than observed in linear analogues, while the activation energy to dissociate UPy–UPy bonds (41–47 kJ/mol) remains mostly unchanged. Longer side chains result in a competition between reducing Tg and inducing entanglements that influence hydrogen-bonded network dynamics. Increasing the backbone length extends the sticky Rouse region without affecting the network modulus (Gx) or UPy–UPy dissociation time (τs). Gx scales linearly with p and ranges from 27 kPa to 1.6 MPa, while τs remains nearly constant in contrast to linear telechelic ionomers, implying a similar self-healability across bottlebrush networks containing different amounts of UPy. These stretchable networks with p ≤ 0.25 undergo self-healing upon repeated rupture and melt pressing at ≤100 °C while retaining similar tensile properties. In summary, decorating bottlebrush polymers with hydrogen bonds creates opportunities to independently manipulate associative network dynamics and mechanical moduli.

Poly(vinyl alcohol) Molecular Bottlebrushes Nucleate Ice.

Ice binding proteins (IBP) have evolved to limit the growth of ice but also to promote ice formation by ice-nucleating proteins (INPs). IBPs, which modulate these seemingly distinct processes, often have high sequence similarities, and molecular size/assembly is hypothesized to be a crucial determinant. There are only a few synthetic materials that reproduce INP function, and rational design of ice nucleators has not been achieved due to outstanding questions about the mechanisms of ice binding. Poly(vinyl alcohol) (PVA) is a water-soluble synthetic polymer well known to effectively block ice recrystallization, by binding to ice. Here, we report the synthesis of a polymeric ice nucleator, which mimics the dense assembly of IBPs, using confined ice-binding polymers in a high-molar-mass molecular bottlebrush. Poly(vinyl alcohol)-based molecular bottlebrushes with different side-chain densities were synthesized via a combination of ring-opening metathesis polymerization (ROMP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization, using "grafting-to" and "grafting-through" approaches. The facile preparation of the PVA bottlebrushes was performed via selective hydrolysis of the acetate of the poly(vinyl acetate) (PVAc) side chains of the PVAc bottlebrush precursors. Ice-binding polymer side-chain density was shown to be crucial for nucleation activity, with less dense brushes resulting in colder nucleation than denser brushes. This bio-inspired approach provides a synthetic framework for probing heterogeneous ice nucleation and a route toward defined synthetic nucleators for biotechnological applications.

Self-Assembly of Repetitive Segment and Random Segment Polymer Architectures.

Recent advances in chemical synthesis have created new methodologies for synthesizing sequence-controlled synthetic polymers, but rational design of monomer sequence for desired properties remains challenging. In this work, we synthesize periodic polymers with repetitive segments using a sequence-controlled ring-opening metathesis polymerization (ROMP) method, which draws inspiration from proteins containing repetitive sequence motifs. The repetitive segment architecture is shown to dramatically affect the self-assembly behavior of these materials. Our results show that polymers with identical repetitive sequences assemble into uniform spherical nanoparticles after thermal annealing, whereas copolymers with random placement of segments with different sequences exhibit disordered assemblies without a well-defined morphology. Overall, these results bring a new understanding to the role of periodic repetitive sequences in polymer assembly.

Core-Shell Gyroid in ABC Bottlebrush Block Terpolymers.

Block polymer self-assembly provides a versatile platform for creating useful materials endowed with three-dimensional periodic network morphologies that support orthogonal physical properties such as high ionic conductivity and a high elastic modulus. However, coil configurations limit conventional linear block polymers to finite ordered network dimensions, which are further restricted by slow self-assembly kinetics at high molecular weights. A bottlebrush architecture can circumvent both shortcomings owing to extended backbone configurations due to side chain crowding and molecular dynamics substantially free of chain entanglements. However, until now, network morphologies have not been reported in AB bottlebrush block copolymers, notwithstanding favorable mean-field predictions. We explored the phase behavior by small-angle X-ray scattering of 133 poly(ethylene-alt-propylene)-b-polystyrene (PEP-PS) diblock and PEP-PS-PEO triblock bottlebrush copolymers prepared by ring-opening metathesis polymerization (ROMP) of norbornene-functionalized poly(ethylene-alt-propylene) (PEP), poly(styrene) (PS), and poly(ethylene oxide) (PEO) macromonomers with total backbone degrees of polymerization Nbb between 20 and 40. The PEP-PS diblocks exhibited only cylindrical and lamellar morphologies over the composition range of ca. 30-70%. However, addition of variable-length bottlebrush PEO blocks to diblocks containing 30-50% PS led to the formation of a substantial core-shell double gyroid (GYR) phase window containing 20 bottlebrush triblock specimens, which is the focus of this report. Encouragingly, the GYR unit cell dimensions increased as d ∼ Nbb0.92, portending the ability to access larger network dimensions than previously obtained with linear AB or ABC block polymers. This work highlights extraordinary opportunities associated with applying facile ROMP chemistry to multiblock bottlebrush polymers.

The Impact of Polymerization Chemistry on the Mechanical Properties of Poly(dimethylsiloxane) Bottlebrush Elastomers.

We compare the low-strain mechanical properties of bottlebrush elastomers (BBEs) synthesized using ring-opening metathesis and free radical polymerization. Through comparison of experimentally measured elastic moduli and those predicted by an ideal, affine model, we evaluate the efficiency of our networks in forming stress-supporting strands. This comparison allowed us to develop a structural efficiency ratio that facilitates the prediction of mechanical properties relative to polymerization chemistry (e.g., softer BBEs when polymerizing under dilute conditions). This work highlights the impact that polymerization chemistry has on the structural efficiency ratio and the resultant mechanical properties of BBEs with identical side chains, providing another "knob" by which to control polymer network properties.

A modular and efficient synthetic platform for the construction of supramolecular mono-telechelic polymers

Supramolecular telechelic polymers are intriguing macromolecular systems for the construction of complex supramolecular systems and responsive soft materials. In this work, we report a practical synthetic approach to preparing supramolecular mono-telechelic polymers with high efficiency and modularity. With a combination of in situ catalyst functionalization, ring-opening metathesis polymerization, and post-polymerization modification, a series of supramolecular mono-telechelic polymers with different supramolecular end-groups and sidechains are synthesized. Several selected examples are then discussed in detail to demonstrate their potential in constructing hierarchical supramolecular architectures, adaptive materials, and supramolecular biomaterials. It is highly anticipated that the synthetic approach reported here will provide rapid and controlled access to complex supramolecular polymeric systems with tailored functions.