Post-polymerization Modification Reactions Research Articles

An Expedient Route to Bio-Based Polyacrylate Alternatives with Inherent Post-Chemical Modification and Degradation Capabilities by Organic Catalysis for Polymerization of Muconate Esters.

The quest for polymers that would be at the same time bio-based and degradable after usage, in addition to offering chemical post-modification options, remains a daunting challenge in contemporary polymer science. Despite advances in polymer chemistry, attempts at controlling the chain-growth polymerization of muconate esters remain unexplored. Here we show that dialkyl muconates can be rapidly polymerized by organocatalyzed group transfer polymerization (O-GTP). O-GTP is conducted to completion at room temperature in toluene within a few minutes, using 1-ethoxy-1-(trimethylsiloxy)-1,3-butadiene (ETSB) as initiator and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylidenamino]-2 5,4 5 catenadi(phosphazene) (P4-t-Bu) as catalyst. Chain extension experiments and synthesis of all muconate-type block copolymers can also be achieved. Furthermore, polymuconates are amenable to facile post-polymerization modification reactions. This is showcased through the hydrolysis of the ester side chains leading to well-defined poly(muconic acid), and by epoxidation of the C=C double bonds of the main chain. Last but not least, these internal alkene groups can be selectively cleaved by ozonolysis, demonstrating the upcyclability of polymuconates under oxidative conditions. This work demonstrates that polymuconates constitute a unique platform of bio-based polymers, easily modifiable in addition to being chemically degradable under user friendly experimental conditions.

Structural and optical properties of hybrid materials derived from gold nanoparticles in different polystyrene (PS)-b-poly(4-vinylpyridine) (P4VP) matrices

We introduce the preparation as well as the structural and optical properties of hybrid materials consisting of diblock copolymer matrices with gold nanoparticles. Anionically synthesized diblock copolymers of the PS-b-P4VP sequence, where PS: polystyrene and P4VP: poly(4-vinylpyridine) with well-defined characteristics were utilized as the polymer matrices. The specific pyridine-containing copolymers were selected due to their susceptibility to post-polymerization chemical modification reactions. Basic tertiary amines can be easily modified due to the presence of the nitrogen atom (N) in the 4-position (-para) of the aromatic ring in the monomeric units of poly(4-vinylpyridine). In this manner, the addition of either atoms or whole compounds as ion pairs is enabled. We report that the role of noble metal atoms in polymer matrices is dual. Firstly, microphase separation in the presence of heteroatoms occurs even in cases of extremely low molecular characteristics due to the increased repulsion between the components and secondly the excitation of plasmon resonance at the polymer/nanoparticle interface is induced. We believe that our work sheds light on the driving forces of self-assembly on the studied modified copolymers. The results strongly suggest that the hybrid materials can adopt well-defined morphologies even in very low molecular weights, a fact that renders them promising candidates for photonic applications.

Synthesis and Structural Insight into poly(dimethylsiloxane)-b-poly(2-vinylpyridine) Copolymers.

In this study, the use of anionic polymerization for the synthesis of living poly(dimethylsiloxane) or PDMS-Li+, as well as poly(2-vinylpyridine) or P2VP-Li+ homopolymers, and the subsequent use of chlorosilane chemistry in order for the two blocks to be covalently joined leading to PDMS-b-P2VP copolymers is proposed. High vacuum manipulations enabled the synthesis of well-defined materials with different molecular weights (Μ¯n, from 9.8 to 36.0 kg/mol) and volume fraction ratios (φ, from 0.15 to 0.67). The Μ¯n values, dispersity indices, and composition were determined through membrane/vapor pressure osmometry (MO/VPO), size exclusion chromatography (SEC), and proton nuclear magnetic resonance spectroscopy (1H NMR), respectively, while the thermal transitions were determined via differential scanning calorimetry (DSC). The morphological characterization results suggested that for common composition ratios, lamellar, cylindrical, and spherical phases with domain periodicities ranging from approximately 15 to 39 nm are formed. A post-polymerization chemical modification reaction to quaternize the nitrogen atom in some of the P2VP monomeric units in the copolymer with the highest P2VP content, and the additional characterizations through 1H NMR, infrared spectroscopy, DSC, and contact angle are reported. The synthesis, characterization, and quaternization of the copolymer structure are important findings toward the preparation of functional materials with enhanced properties suitable for various nanotechnology applications.

Non-activated Esters as Reactive Handles in Direct Post-Polymerization Modification.

Non-activated esters are prominently featured functional groups in polymer science, as ester functional monomers display great structural diversity and excellent compatibility with a wide range of polymerization mechanisms. Yet, their direct use as a reactive handle in post-polymerization modification has been typically avoided due to their low reactivity, which impairs the quantitative conversion typically desired in post-polymerization modification reactions. While activated ester approaches are a well-established alternative, the modification of non-activated esters remains a synthetic and economically valuable opportunity. In this review, we discuss past and recent efforts in the utilization of non-activated ester groups as a reactive handle to facilitate transesterification and aminolysis/amidation reactions, and the potential of the developed methodologies in the context of macromolecular engineering.

Thermal and Bulk Properties of Triblock Terpolymers and Modified Derivatives towards Novel Polymer Brushes.

We report the synthesis of three (3) linear triblock terpolymers, two (2) of the ABC type and one (1) of the BAC type, where A, B and C correspond to three chemically incompatible blocks such as polystyrene (PS), poly(butadiene) of exclusively (~100% vinyl-type) -1,2 microstructure (PB1,2) and poly(dimethylsiloxane) (PDMS) respectively. Living anionic polymerization enabled the synthesis of narrowly dispersed terpolymers with low average molecular weights and different composition ratios, as verified by multiple molecular characterization techniques. To evaluate their self-assembly behavior, transmission electron microscopy and small-angle X-ray scattering experiments were conducted, indicating the effect of asymmetric compositions and interactions as well as inversed segment sequence on the adopted morphologies. Furthermore, post-polymerization chemical modification reactions such as hydroboration and oxidation were carried out on the extremely low molecular weight PB1,2 in all three terpolymer samples. To justify the successful incorporation of -OH groups in the polydiene segments and the preparation of polymeric brushes, various molecular, thermal, and surface analysis measurements were carried out. The synthesis and chemical modification reactions on such triblock terpolymers are performed for the first time to the best of our knowledge and constitute a promising route to design polymers for nanotechnology applications.

Alternating styrene-propylene and styrene-ethylene copolymers prepared by photocatalytic decarboxylation.

Synthesis of olefin-styrene copolymers with defined architecture is challenging due to the limitations associated with the inherent reactivity ratios for these monomers in radical or metal-catalyzed polymerizations. Herein, we developed a straightforward approach to alternating styrene-propylene and styrene-ethylene copolymers by combining radical polymerizations and powerful post-polymerization modification reactions. We employed reversible addition-fragmentation chain transfer (RAFT) copolymerization between styrene derivatives and saccharin (meth)acrylamide to generate alternating copolymers. Once polymerized, the amide bond of the saccharin monomers was highly reactive toward hydrolysis, an observation exploited to obtain alternating styrene-acrylic acid/methacrylic acid copolymers. Subsequent mild decarboxylation of the (meth)acrylic acid groups in the presence of a photocatalyst and a hydrogen source under visible light resulted in the styrene-alt-ethylene/propylene copolymers. Alternating copolymers comprised of either propylene or ethylene units alternating with functional styrene derivatives were also prepared, illustrating the compatibility of this approach for functional polymer synthesis. Finally, the thermal properties of the alternating copolymers were compared to those from statistical copolymer analogs to elucidate the effect of microarchitecture and styrene substituents on the glass transition temperature.

Synthesis and Characterization of Regioselectively Functionalized Mono-Sulfated and -Phosphorylated Anionic Poly-Amido-Saccharides.

Polysaccharides are abundant in nature and employed in various biomedical applications ranging from scaffolds for tissue engineering to carriers for drug delivery systems. However, drawbacks such as tedious isolation protocols, contamination, batch-to-batch consistency, and lack of compositional control with regards to stereo- and regioselectivity impede the development and utility of polysaccharides, and thus mimetics are highly sought after. We report a synthetic strategy to regioselectively functionalize poly-amido-saccharides with sulfate or phosphate groups using post-polymerization modification reactions. Orthogonally protected β-lactam monomers, synthesized from D-glucal, undergo anionic ring-opening polymerization to yield polymers with degrees of polymerization of 12, 25, and 50. Regioselective deprotection followed by functionalization and global deprotection affords the sulfated and phosphorylated poly-amido-saccharides. The resulting anionic polymers are water soluble and non-cytotoxic and adopt helical conformations. This new methodology provides access to otherwise inaccessible functional polysaccharide mimetics for biomedical applications.

Vertical Alignment of Liquid Crystal on Sustainable 2,4-Di-tert-butylphenoxymethyl-Substituted Polystyrene Films.

We synthesized sustainable 2,4-di-tert-butylphenoxymethyl-substituted polystyrenes (PDtBP#, # = 88, 68, 35, and 19, where # is molar percent contents of 2,4-di-tert-butylphenoxymethyl moiety), using post-polymerization modification reactions in order to study their liquid crystal (LC) alignment behaviors. In general, LC cells fabricated using polymer film with higher molar content of 2,4-di-tert-butylphenoxymethyl side groups showed vertical LC alignment behavior. LC alignment behavior in LC cell was related to the surface energy of the polymer alignment layer. For example, when the total surface energy value of the polymer layer was smaller than about 29.4 mJ/m2, vertical alignment behaviors were observed, generated by the nonpolar 2,4-di-tert-butylphenoxymethyl moiety with long and bulky carbon groups. Orientation stability was observed at 200 °C in the LC cells fabricated using PDtBP88 as the LC alignment layer. Therefore, as a natural compound modified polymer, PDtBP# can be used as a candidate LC alignment layer for environmentally friendly applications.

One-pot cascade polycondensation and Passerini three-component reactions for the synthesis of functional polyesters

A one-pot cascade four-component polymerization and post-polymerization modification reaction is introduced to synthetic polymer chemistry.

Fast-track computational access to reaction mechanisms provides comprehensive insights into aminolysis postpolymerization modification reactions

Activated esters commonly used in polymer synthesis have been systematically characterized at the DLPNO-CCSD(T) level of theory by taking advantage of the recently developed semiempirical method of GFN2-xTB.

Surface-Initiated, Catechol-Containing Polymer Films for Effective Chelation of Aluminum Ions.

We present a new route for obtaining surface-tethered polymer films containing pendant catechol functional groups via surface-initiated activators regenerated by electron-transfer atom-transfer radical polymerization (SI-ARGET ATRP) of glycidyl methacrylate (GMA) and post-polymerization modification of the resulting poly(glycidyl methacrylate) (pGMA) films with dopamine. This method enables a high degree of functionalization of pGMA films with catechol groups at a controlled level, depending on the duration of the post-polymerization modification reaction. The dopamine-pGMA films readily absorbs Al3+ and Zn2+ ions, as verified by quartz crystal microbalance with dissipation (QCM-D) under continuous flow conditions, and demonstrates a four-fold molar selectivity to Al3+ over Zn2+. The ions desorb from the films upon rinsing with pure deionized (DI) water, which regenerates the catechol sites in the dopamine-pGMA film. Subsequent exposure to metal ions after rinsing steps yields reproducible levels of loading.

Fundamental insights into aminolysis postpolymerization modification reaction of polymers featuring α,α-Difluoroacetate Esters

Detailed experimental insight into aminolysis postpolymerization modification reactions of polymers featuring α,α-difluoroacetates is provided to elucidate the synthetic scope of postpolymerization modifications. By combining the Friedel-Crafts polycondensation and the aminolysis post-polymerization modification, polymers with a rigid triphenylmethane backbone were chemically modified with acid sensitive functional units with high ester conversions (up to > 95%). Primary amines were found to be significantly more efficient in aminolysis than secondary amines. Thermal properties of polymers featuring α,α-difluoroacetates and α,α-difluoroacetamides were analyzed experimentally and their model systems were studied computationally. It was found that the aminolysis postpolymerization modification reactions of polymers with the rigid triphenylmethane backbone has no negative influence on their thermal properties. This indicates that α,α-difluoroacetate aminolysis studied herein offers a feasible and useful synthetic tool in postpolymerization modifications.

Recent Advances in Thermoresponsive OEGylated Poly(amino acid)s.

Thermoresponsive polymers have been widely studied in the past decades due to their potential applications in biomedicine, nanotechnology, and so on. As is known, poly(N-isopropylacrylamide) (PNIPAM) and poly(oligo(ethylene glycol)methacrylates) (POEGMAs) are the most popular thermoresponsive polymers, and have been studied extensively. However, more advanced thermoresponsive polymers with excellent biocompatibility, biodegradability, and bioactivity also need to be developed for biomedical applications. OEGylated poly(amino acid)s are a kind of novel polymer which are synthesized by attaching one or multiple oligo(ethylene glycol) (OEG) chains to poly(amino acid) (PAA).These polymers combine the great solubility of OEG, and the excellent biocompatibility, biodegradability and well defined secondary structures of PAA. These advantages allow them to have great application prospects in the field of biomedicine. Therefore, the study of OEGylated poly(amino acid)s has attracted more attention recently. In this review, we summarized the development of thermoresponsive OEGylated poly(amino acid)s in recent years, including the synthesis method (such as ring-opening polymerization, post-polymerization modification, and Ugi reaction), stimuli-response behavior study, and secondary structure study. We hope that this periodical summary will be more conducive to design, synthesis and application of OEGylated poly(amino acid)s in the future.

Synthesis and Post‐Polymerization Modification of Poly(N‐(4‐Vinylphenyl)Sulfonamide)s

Frontispiece: In article number 2100063 by Patrick Theato, Hatice Mutlu, and Edgar Molle, a set of novel poly(N-(4-vinylphenyl)sulfonamide) s featuring varying electron densities is prepared in a straightforward fashion and subsequently used in post-polymerization modification reactions via aza-Michael addition with different electron-defi cient alkenes as Michael acceptors for the facile synthesis of polymeric protected -amino acid derivatives.

Stereoselective Diels-Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers.

Although gem-diborylalkenes are known to be among the most valuable reagents in modern organic synthesis, providing a rapid access to a wide array of transformations, including the construction of C–C and C-heteroatom bonds, their use as dienophile-reactive groups has been rare. Herein we report the Diels–Alder (DA) reaction of (unsymmetrical) gem-diborylalkenes. These reactions provide a general and efficient method for the stereoselective conversion of gem-diborylalkenes to rapidly access 1,1-bisborylcyclohexenes. Using the same DA reaction manifold with borylated-dienes and gem-diborylalkenes, we also developed a concise, highly regioselective synthesis of 1,1,2-tris- and 1,1,3,4-tetrakis(boronates)cyclohexenes, a family of compounds that currently lack efficient synthetic access. Furthermore, DFT calculations provided insight into the underlying factors that control the chemo-, regio-, and stereoselectivity of these DA reactions. This method also provides stereodivergent syntheses of gem-diborylnorbornenes. The utility of the gem-diborylnorbornene building blocks was demonstrated by ring-opening metathesis polymerization (ROMP), providing a highly modular approach to the first synthesis of the gem-diboron-based polymers. Additionally, these polymers have been successfully submitted to postpolymerization modification reactions. Given its simplicity and versatility, we believe that this novel DA and ROMP approach holds great promise for organoboron synthesis as well as organoboron-based polymers and that it will result in more novel transformations in both academic and industrial research.

Construction of ring-based architectures via ring-expansion cationic polymerization and post-polymerization modification: design of cyclic initiators from divinyl ether and dicarboxylic acid

Topologically unique polymers such as tadpole and figure-eight polymers were synthesized via ring-expansion cationic polymerization (RECP) of vinyl ether with a functionalized cyclic initiator, followed by post-polymerization modification (PPM) reactions.

Computer-Aided Design of Postpolymerization Modification Reaction Based on Aminolysis of α,α-Difluoroacetate Esters

A new postpolymerization protocol based on the reactivity of α,α-difluoroacetate esters is proposed and rationalized via a combined effort of computational and experimental methods. Reaction system...

Stoichiometric Control over Partial Transesterification of Polyacrylate Homopolymers as Platform for Functional Copolyacrylates.

Only recently, post-polymerization modification reactions of unactivated polyacrylates have been emerging as an attractive alternative to utilizing reactive monomers, enabling the synthetic upcycling of these widely applied polymers. Within this contribution, the triazabicyclodecene-catalyzed transesterification of polyacrylates is reported, including the reaction kinetics and the broad scope for macromolecular design of functional copolyacrylates. More specifically, the transesterification is performed under equilibrium conditions with a set of primary alcohols whereby the reaction kinetics and the obtained conversion as a function of stoichiometric excess of alcohol are evaluated. The results show that the obtained conversion is dependent on the polarity of the solvent and of the alcohol. Through this approach, the transesterification degree can be accurately controlled by stoichiometry, enabling the precise modulation of the macromolecular structure. Finally, the utility of this approach is demonstrated to incorporate functional side chains that are incompatible with radical polymerization, to facilitate Diels-Alder and thiol-ene reactions, enabling access to a broad range of functional materials from simple polyacrylate homopolymer precursors.

Correction: Flow-facilitated ring opening metathesis polymerization (ROMP) and post-polymerization modification reactions

Correction for ‘Flow-facilitated ring opening metathesis polymerization (ROMP) and post-polymerization modification reactions’ by Selesha I. Subnaik et al., Polym. Chem., 2019, 10, 4524–4528, DOI: 10.1039/C9PY00822E

The dawn of polymer chemistry based on multicomponent reactions

This focus review documents the developments in polymer synthesis that involve multicomponent reactions (MCRs) and related sequential reaction systems. Postpolymerization modification and step-growth polymerization reactions based on MCRs and sequential reactions such as the Kabachnik–Fields three-component reaction (KF-3CR) are described. Welcoming more participants in a polymer synthesis; recent years, multicomponent reactions (MCRs) have been gradually integrated into synthetic polymer chemistry, which led to a new synthetic toolbox for a range of interdisciplinary applications. In this focus review, this new trend in polymer chemistry has been summarized with including contributions from the author.