Sequential Ring-opening Polymerization Research Articles

Polymers from Plant Oils Linked by Siloxane Bonds for Programmed Depolymerization.

The increased production of plastics is leading to the accumulation of plastic waste and depletion of limited fossil fuel resources. In this context, we report a strategy to create polymers that can undergo controlled depolymerization by linking renewable feedstocks with siloxane bonds. α,ω-Diesters and α,ω-diols containing siloxane bonds were synthesized from an alkenoic ester derived from castor oil and then polymerized with varied monomers, including related biobased monomers. In addition, cyclic monomers derived from this alkenoic ester and hydrosiloxanes were prepared and cyclized to form a 26-membered macrolactone containing a siloxane unit. Sequential ring-opening polymerization of this macrolactone and lactide afforded an ABA triblock copolymer. This set of polymers containing siloxanes underwent programmed depolymerization into monomers in protic solvents or with hexamethyldisiloxane and an acid catalyst. Monomers afforded by the depolymerization of polyesters containing siloxane linkages were repolymerized to demonstrate circularity in select polymers. Evaluation of the environmental stability of these polymers toward enzymatic degradation showed that they undergo enzymatic hydrolysis by a fungal cutinase from Fusarium solani. Evaluation of soil microbial metabolism of monomers selectively labeled with 13C revealed differential metabolism of the main chain and side chain organic groups by soil microbes.

Amphiphilic block copolymers bearing fatty acid derivatives as vehicles for THC in the development of analgesic oral formulations

Cannabis-based therapeutics have gained increasing attention for their potential health benefits; however, the efficient administration of hydrophobic constituents such as Δ9-tetrahydrocannabinol (THC) remains a challenge. This study explores a novel approach employing amphiphilic block copolymers to encapsulate a THC-rich extract to enhance its analgesic effect. The synthesis of amphiphilic block copolymers involves sequential ring-opening polymerization of caprolactone and a cyclic carbonate with pedant alkyne moieties. This is followed by an alkyne/azide click reaction with fatty acid derivatives. These copolymers are used to encapsulate the THC-rich extract. These extract-loaded micelles exhibit nanometric sizes, uniform distribution, and high colloidal stability in simulated gastrointestinal fluids. The release kinetic assessment of THC from the micelles displays controlled and sustained profiles, which are influenced by the hydrophobic nature of the copolymer core. In vivo evaluations using a murine model revealed the safety of micellar formulations, with minimal impact on behavior and organ health. Remarkably, micellar systems demonstrated prolonged analgesic effects in both mechanical and chemical pain models, outperforming nonencapsulated THC. This study introduces a pioneering approach to cannabis-based analgesics with prolonged activity, harnessing the potential of the tailored design of amphiphilic block copolymers to enhance the delivery and efficacy of hydrophobic cannabinoids.

PH-Dependent Solution Micellar Structure of Amphoteric Polypeptoid Block Copolymers with Positionally Controlled Ionizable Sites.

While solution micellization of ionic block copolymers (BCP) with randomly distributed ionization sites along the hydrophilic segments has been extensively studied, the roles of positionally controlled ionization sites along the BCP chains in their micellization and resulting micellar structure remain comparatively less understood. Herein, three amphoteric polypeptoid block copolymers carrying two oppositely charged ionizable sites, with one fixed at the hydrophobic terminus and the other varyingly positioned along the hydrophilic segment, have been synthesized by sequential ring-opening polymerization method. The presence of the ionizable site at the hydrophobic segment terminus is expected to promote polymer association toward equilibrium micellar structures in an aqueous solution. The concurrent presence of oppositely charged ionizable sites on the polymer chains allows the polymer association to be electrostatically modulated in a broad pH range (ca. 2-12). Micellization of the amphoteric polypeptoid BCP in dilute aqueous solution and the resulting micellar structure at different solution pHs was investigated by a combination of scattering and microscopic methods. Negative-stain transmission-electron microscopy (TEM), small-angle neutron scattering (SANS), and small-angle X-ray scattering (SAXS) analyses revealed the dominant presence of core-shell-type spherical micelles and occasional rod-like micelles with liquid crystalline (LC) domains in the micellar core. The micellar structures (e.g., aggregation number, radius of gyration, chain packing in the micelle) were found to be dependent on the solution pH and the position of the ionizable site along the chain. This study has highlighted the potential of controlling the position of ionizable sites along the BCP polymer to modulate the electrostatic and LC interactions, thus tailoring the micellar structure at different solution pH values in water.

Mixed shell nanoparticles via polymerization-induced self-assembly of Y-shaped ABC miktoarm star copolymers

Mixed shell polymer nanoparticles (MSPNs) have emerged as a very significant research topic in the field of macromolecular science. In this study, a robust method for efficient preparation of MSPNs with various morphologies via polymerization-induced self-assembly (PISA) of Y-shaped ABC miktoarm star copolymers was demonstrated. Poly(ε-caprolactone)-b-poly(methyl methacrylate) diblock copolymers carrying a trithiocarbonate (TTC) group at the diblock joint (PCL-TTC-PMMA) were synthesized via the sequential ring-opening polymerization of ε-caprolactone (ε-CL) and atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) using a multifunctional initiator. Subsequently, PCL-TTC-PMMA copolymers acted as both macromolecular chain transfer agents (CTAs) and stabilizers to mediate reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of 4-vinylpyridene (4-VP) in toluene, producing MSPNs with different morphologies including spheres, short rods, worms and vesicles. The factors influencing the morphologies of MSPNs during PISA, including solid content and the chain length of stabilizers, were investigated. RAFT-based dispersion polymerizations of 4-VP monomers mediated by PCL-TTC-PMMA copolymers were also compared with those mediated by linear PMMA-TTC with approximately the same length of PCL-TTC-PMMA under the identical conditions. Their different PISA behaviors were unraveled.

Efficient Synthesis and PISA Behavior of Molecular Bottlebrush Block Copolymers via a Grafting-From Strategy through RAFT Dispersion Polymerization

Precise synthesis of molecular bottlebrushes (MBBs) with high yield via the grafting-from strategy using a reversible deactivation radical polymerization (RDRP) technique has remained elusive. Herein, the molecular bottlebrush block copolymers (MBB BCPs) with high yield and varying chemical compositions were synthesized via a polymerization-induced self-assembly (PISA)-assisted grafting-from strategy by reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization. First, the poly(norbornene-g-poly(ethylene oxide))-b-poly(norbornene-g-chain transfer agent) [P(NB-g-PEG45)-b-P(NB-CTA)] BCPs with varied chemical compositions were synthesized by sequential ring-opening metathesis polymerization (ROMP) of norbornene PEG macromonomers (NB-PEG45) and norbornene chain transfer agent (NB-CTA) monomers. Subsequently, these P(NB-g-PEG45)m-b-P(NB-CTA)n BCPs were used as multifunctional macro-CTAs for the synthesis of MBB BCPs with a high yield (up to 80% styrene monomer conversion) and a low dispersity (Đ < 1.15) via a grafting-from strategy through RAFT dispersion polymerization. The PISA behaviors of these MBB BCPs were also investigated, and the results indicated that the MBB BCPs assemblies were transformed from spherical micelles into two-dimensional disk-like micelles because the rigidity of the PS MBB segment increased with the growth of PS side chains.

PLA‐b‐SMA as an Amphiphilic Diblock Copolymer for Encapsulation of Lipophilic Cargo

AbstractThe encapsulation of active pharmaceutical ingredients (APIs) within drug delivery systems such as polymeric nanoparticles (PNPs) vastly improves the therapeutic efficiency of the incorporated APIs. PNPs synthesized using amphiphilic block copolymers are efficient drug delivery systems as the hydrophobic block facilitates the encapsulation of lipophilic components and the hydrophilic block constitutes the hairy corona of the PNP that stabilizes the nanocarriers against aggregation in solution. Poly(styrene‐alt‐maleic acid) (SMA) is an attractive polymer for the hydrophilic corona of PLA‐based nanoparticles as it allows for post polymerization functionalization and aids in the prevention of NP aggregation. The synthesis of a novel PLA‐b‐SMA block copolymer, via sequential ring opening polymerization (ROP) and reversible addition–fragmentation chain transfer (RAFT) polymerization, is presented. PLA macro‐CTAs, synthesized via ROP, can be chain extended via RAFT copolymerization of styrene and maleic anhydride to yield PLA‐b‐SMAnh and via RAFT polymerization of N‐vinylpyrrolidone to yield PLA‐b‐PVP block copolymers. Controlled hydrolysis of the anhydride moieties converts PLA‐b‐SMAnh into PLA‐b‐SMA. Monodisperse PLA‐b‐SMA and PLA‐b‐PVP nanoparticles (NPs) ranging in diameter between 60 and 220 nm are prepared. The lipophilic fluorescent dye DiI is encapsulated within the NPs successfully and these fluorescent NPs are used in a preliminary cell uptake study.

Degradable, Photochemically Printable Poly(propylene fumarate)-Based ABA Triblock Elastomers.

Additive manufacturing is rapidly advancing tissue engineering, but the scope of its clinical translation is limited by a lack of materials designed to meet specific mechanical properties and resorption timelines. Materials that are printable via photochemical cross-linking, fully degradable, and elastomeric have proven to be particularly challenging to develop. Herein, we report the synthesis of a series of poly(propylene fumarate-b-γ-methyl-ε-caprolactone-b-propylene fumarate) ABA triblock polymers using sequential ring-opening polymerization and ring-opening copolymerization. When cross-linked photochemically using a continuous liquid interface production digital light processing Carbon M2 printer, these ABA-type triblock copolymers are durable elastomers with tunable degradation and elastic properties. The polymers are shown to undergo slow, hydrolytic degradation in vitro with minimal loss of mechanical performance during degradation.

Synthesis and Micellization of Bottlebrush Poloxamers.

Bottlebrush polymers are characterized by an expansive parameter space, including graft length and spacing along the backbone, and these features impact various structural and physical properties such as molecular diffusion and bulk viscosity. In this work, we report a synthetic strategy for making grafted block polymers with poly(propylene oxide) and poly(ethylene oxide) side chains, bottlebrush analogues of poloxamers. Combined anionic and sequential ring-opening metathesis polymerization yielded low dispersity polymers, at full conversion of the macromonomers, with control over graft length, graft end-groups, and overall molecular weight. A set of bottlebrush poloxamers (BBPs), with identical graft lengths and composition, was synthesized over a range of molecular weights. Dynamic light scattering and transmission electron microscopy were used to characterize micelle formation in aqueous buffer. The critical micelle concentration scales exponentially with overall molecular weight for both linear and bottlebrush poloxamers; however, the bottlebrush architecture shifts micelle formation to a much higher concentration at a comparable molecular weight. Consequently, BBPs can exist in solution as unimers at significantly higher molecular weights and concentrations than the linear analogues.

Rapid and Controlled Polymerization of Bio-sourced δ-Caprolactone toward Fully Recyclable Polyesters and Thermoplastic Elastomers.

The development of chemically recyclable polymers presents the most appealing solution to address the plastics' end-of-use problem. Despite the recent advancements, it is highly desirable to develop chemically recyclable polymers from commercially available monomers to avoid the costly and time-consuming commercialization. In this contribution, we achieve the controlled ring-opening polymerization (ROP) of bio-sourced δ-caprolactone (δCL) using strong base/urea binary catalysts. The obtained PδCL is capable of chemical recycling to δCL in an almost quantitative yield by thermolysis. Sequential ROP of δCL and l-lactide (l-LA) affords well-defined PLLA-b-PδCL-b-PLLA triblock copolymers, which behave as thermoplastic elastomers with excellent elastic recovery, tensile strength and ultimate elongation. The upcycling of PLLA-b-PδCL-b-PLLA to recover ethyl lactate and δCL with high yields is achieved by refluxing with ethanol and then distillation under reduced pressure.

Rapid and Controlled Polymerization of Bio‐sourced δ‐Caprolactone toward Fully Recyclable Polyesters and Thermoplastic Elastomers

AbstractThe development of chemically recyclable polymers presents the most appealing solution to address the plastics’ end‐of‐use problem. Despite the recent advancements, it is highly desirable to develop chemically recyclable polymers from commercially available monomers to avoid the costly and time‐consuming commercialization. In this contribution, we achieve the controlled ring‐opening polymerization (ROP) of bio‐sourced δ‐caprolactone (δCL) using strong base/urea binary catalysts. The obtained PδCL is capable of chemical recycling to δCL in an almost quantitative yield by thermolysis. Sequential ROP of δCL and l‐lactide (l‐LA) affords well‐defined PLLA‐b‐PδCL‐b‐PLLA triblock copolymers, which behave as thermoplastic elastomers with excellent elastic recovery, tensile strength and ultimate elongation. The upcycling of PLLA‐b‐PδCL‐b‐PLLA to recover ethyl lactate and δCL with high yields is achieved by refluxing with ethanol and then distillation under reduced pressure.

Synthesis and self-assembly of amphiphilic diblock polycarbonates with various pendant hydrophilic groups

Self-assembled micro-paricles have been proven to be efficient microcarriers for delivering various therapeutic agents. Polycarbonates have demonstrated excellent biodegradability and biocompatibility as material for polymeric microcarriers. A diblock polycarbonate with tunable block length and active sites is synthesized via one-pot sequential ring-opening polymerization (ROP). The polymer acts as a material platform for versatile modifications to prepare a series of amphiphilic diblock polycarbonates which can self-assemble into microparticles. The effect of different hydrophilic pendent groups controlling the morphology and surface charge of the assemblies is systematically investigated. The non-equilibrium spherical particles with varying sizes are formed in one day, and the spheres can further assemble into multi-compartments vesicles (MCVs). Cationic, anionic or neutral carriers can be prepared depending on the type of pendant groups attached. The versatile amphiphilic copolymer assemblies have good potential in biomedical applications.

Thermoreversible poly(trimethylene carbonate)-based block copolymers containing reactive furfuryl groups via sequential ROP and ATRP

Block copolymers containing poly(trimethylene carbonate) (PTMC) middle block and poly(furfuryl methacrylate) PFMA end blocks were synthesized through sequential organocatalytic ring opening polymerization (ROP) of trimethylene carbonate and thermal and photoinitiated metal-free atom transfer radical polymerizations (ATRP) of furfuryl methacrylate. The thermal and mechanical properties of the triblock copolymers were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamical mechanical analysis (DMA). The crosslinking via Diels-Alder (DA) reaction between the furan groups of the block copolymers and bismaleimide and bisitaconimide was proved by FTIR and DSC and the thermoreversibility properties of the crosslinked polymer were subsequently investigated using DSC and solubility testing.

Cover Image, Volume 138, Issue 42

The cover designed by Wanida Janvikul and co-authors displays an SEM micrograph of a digital light processing (DLP)-printed porous scaffold consisted of poly(caprolactone-co-glycidyl methacrylate). The copolymer was synthesized via sequential ring-opening polymerization of ε-caprolactone and glycidyl methacrylate, which bypassed the usages of substantial chemicals and complicated purification steps. This versatile neat synthetic route explicitly opens up a new method to prepare biodegradable light-assisted 3D printing materials from other biodegradable cyclic ester monomers. DOI: 10.1002/app.51391

Expeditious synthesis of aromatic-free piperidinium-functionalized polyethylene as alkaline anion exchange membranes.

Alkaline anion exchange membranes (AAEMs) with high hydroxide conductivity and good alkaline stability are essential for the development of anion exchange membrane fuel cells to generate clean energy by converting renewable fuels to electricity. Polyethylene-based AAEMs with excellent properties can be prepared via sequential ring-opening metathesis polymerization (ROMP) and hydrogenation of cyclooctene derivatives. However, one of the major limitations of this approach is the complicated multi-step synthesis of functionalized cyclooctene monomers. Herein, we report that piperidinium-functionalized cyclooctene monomers can be easily prepared via the photocatalytic hydroamination of cyclooctadiene with piperidine in a one-pot, two-step process to produce high-performance AAEMs. Possible alkaline-degradation pathways of the resultant polymers were analyzed using spectroscopic analysis and dispersion-inclusive hybrid density functional theory (DFT) calculations. Quite interestingly, our theoretical calculations indicate that local backbone morphology—which can potentially change the Hofmann elimination reaction rate constant by more than four orders of magnitude—is another important consideration in the rational design of stable high-performance AAEMs.

Copolyesters of ε-caprolactone and l-lactide catalyzed by a tetrabutylammonium phthalimide-N-oxyl organocatalyst.

Aliphatic polyesters are biocompatible materials that can be used in biomedical applications. We report here the use of tetrabutylammonium phthalimide-N-oxyl catalyst (TBAPINO), as a thermally stable organocatalyst for the ring-opening polymerization (ROP) of cyclic esters under mild conditions. In the solution ROP of ε-caprolactone (ε-CL), quantitative conversion and Mn of ∼20 000 g mol−1 are achieved in a wide temperature range from −15 to 60 °C. Under bulk condition, the conversion of ε-CL reaches over 85% at 120 °C within 2 h. The living ROP character of l-lactide (l-LA) catalyzed over TBAPINO is proved by multiple additions of monomer in the bulk polymerization. The catalyst shows comparable selectivity towards the ring-opening polymerization of l-LA and ε-CL. Their copolymerization over TBAPINO is carried out in one-pot bulk condition in terms of the reaction time, monomer feed ratio, and sequence of addition. The colorless poly(ε-caprolactone-co-lactide) (PCLA) is obtained with considerable conversion of both monomers with the Mn over 22 000 g mol−1.

Organocatalytic sequential ring-opening polymerization of cyclic ester/epoxide and N-sulfonyl aziridine: metal-free and easy access to block copolymers

Sequential ring-opening polymerization of ε-caprolactone (ε-CL)/propylene oxide (PO) and N-sulfonyl aziridine switched by tosyl isocyanate (TSI) allows the metal-free synthesis of polysulfonamide-based copolymers.

Spherical Photonic Nanostructures from High Molecular Weight Liquid Crystalline Brushlike Block Copolymers

We demonstrate sequential ring-opening metathesis polymerization (ROMP) of norbornene bearing n-alkyloxycyanobiphenyl (NBCB12) and norbornene bearing poly(dl-lactide) (NBPLA) to synthesize low poly...

Crystallization and Alkaline Degradation Behaviors of Poly(l-Lactide)/4-Armed Poly(ε-Caprolactone)-Block-Poly(d-Lactide) Blends with Different Poly(d-Lactide) Block Lengths.

Four-armed poly(ε-caprolactone)-block-poly(d-lactide) (4-C-D) copolymers with different poly(d-lactide) (PDLA) block lengths (Mn,PDLAs) were synthesized by sequential ring-opening polymerization (ROP). The formation of stereocomplex (SC) crystallites in the 80/20 poly(l-lactide) (PLLA)/4-C-D blends were investigated with the change of Mn,PDLA from 0.5 to 1.5 kg/mol. It was found that the crystallization and alkaline degradation of the blends were profoundly affected by the formed SC crystallites. The PLLA/4-C-D0.5 blend had the lowest crystallization rate of the three blends, and it was difficult to see spherulites in this blend by polarized optical microscopy (POM) observation after isothermal crystallization at 140 °C for 4 h. Meanwhile, when Mn,PDLA was 1 kg/mol or 1.5 kg/mol, SC crystallites could be formed in the PLLA/4-C-D blend and acted as nucleators for the crystallization of PLLA homo-crystals. However, the overall crystallization rates of the two blends were still lower than that of the neat PLLA. In the PLLA/4-C-D1.5 blend, the Raman results showed that small isolated SC spherulites were trapped inside the big PLLA homo-spherulites during isothermal crystallization. The degradation rate of the PLLA/4-C-D blend decreased when Mn,PDLA increased from 0.5 to 1.5 kg/mol, and the degradation morphologies had a close relationship with the crystallization state of the blends. This work revealed the gradual formation of SC crystallites with the increase in Mn,PDLA in the PLLA/4-C-D blends and its significant effect on the crystallization and degradation behaviors of the blend films.

Preparation of antimicrobial and biodegradable hybrid soybean oil and poly (ʟ-lactide) based polymer with quaternized ammonium salt

The novel hybrid quaternized soybean oil (SBO) and poly (ʟ-lactide) (PLA) based polymer (QAS-SBO-PLA) is synthesized by sequential ring-opening polymerization (ROP) and nucleophilic substitution reaction. In this purpose, oxirane rings of epoxidized soybean oil (ESBO) firstly are modified to chlorine and hydroxyl functionalities by utilizing hydrochloric acid (Cl-SBO-OH). The obtained Cl-SBO-OH is used as macro-initiator for the ROP of ʟ-lactide monomer in the presence of stannous octoate as a catalyst in order to attain the SBO main chain possessing chlorine and PLA pendant groups (Cl-SBO-PLA). Finally, Cl-SBO-PLA is quaternized by triethyl amine to achieve the corresponding material QAS-SBO-PLA. Structural analysis of QAS-SBO-PLA is performed by Fourier transform infrared (FT-IR) and proton nuclear magnetic resonance (1H NMR) spectroscopies, and gel permeation chromatography (GPC) as well, whereas wettability and thermal properties are determined by water contact angle (WCA) measurement, thermogravimetric (TGA) and differential scanning calorimetry (DSC) analyses, respectively. Antimicrobial activity of QAS-SBO-PLA against to gram positive Staphylococcus aureus (S. aureus) and gram negative E. coli (E. coli) bacteria is investigated by agar diffusion method. Moreover, hydrolytic and enzymatic biodegradation behavior of QAS-SBO-PLA is monitored for 30 days in the presence or absence of lipase enzyme. The results of the present study indicate that QAS-SBO-PLA achieved has higher inhibition effect against to S. aureus than E. coli. Furthermore, approximately 44% of QAS-SBO-PLA by weight is degraded in the enzymatic medium, while this degradation percentage found to be 12% for hydrolytic medium in 30 days. It is thus estimated that this facile synthesis method for QAS-SBO-PLA with good antimicrobial and biodegradation abilities will provide beneficial insights to investigators working on biomedical applications.

Amphiphilic Nucleobase-Containing Polypeptide Copolymers-Synthesis and Self-Assembly.

Nucleobase-containing polymers are an emerging class of building blocks for the self-assembly of nanoobjects with promising applications in nanomedicine and biology. Here we present a macromolecular engineering approach to design nucleobase-containing polypeptide polymers incorporating thymine that further self-assemble in nanomaterials. Diblock and triblock copolypeptide polymers were prepared using sequential ring-opening polymerization of γ-Benzyl-l-glutamate N-carboxyanhydride (BLG-NCA) and γ-Propargyl-l-glutamate N-carboxyanhydride (PLG-NCA), followed by an efficient copper(I)-catalyzed azide alkyne cycloaddition (CuAAc) functionalization with thymidine monophosphate. Resulting amphiphilic copolymers were able to spontaneously form nanoobjects in aqueous solutions avoiding a pre-solubilization step with an organic solvent. Upon self-assembly, light scattering measurements and transmission electron microscopy (TEM) revealed the impact of the architecture (diblock versus triblock) on the morphology of the resulted nanoassemblies. Interestingly, the nucleobase-containing nanoobjects displayed free thymine units in the shell that were found available for further DNA-binding.