Synthesis Of Functional Polymers Research Articles

Bis(imino)pyridyliron incorporated with NO2, F and benzhydryl substituents as thermostable precatalysts for vinyl-terminated polyethylenes

The electronic and steric properties of ligands are of great importance in late transition metal catalyst mediated ethylene polymerization to tune the catalytic performance. In this contribution, strong electron-withdrawing groups—fluoro and nitro—along with benzhydryl as a steric component, were incorporated into the parent bis(imino)pyridine ligand structure to prepare a series of iron (II) chloride complexes: 2-[MeC=N{2-(Ph2CH)-4-NO2-6-F}C6H2]-6-[MeC=N(Ar)C6H2]C5H3N–FeCl2 (Ar = 2,6-Me2C6H3Fe2Me, 2,6-Et2C6H3Fe2Et, 2,6-iPr2C6H3Fe2iPr, 2,4,6-Me3C6H2Fe3Me and 2,6-Et2-4-MeC6H2Fe2Et,Me). Apart from the structural characterization of all complexes executed via FTIR and elemental analysis, X-ray diffraction analysis unveiled distorted square pyramidal geometry for Fe2Me (τ5 = 0.21) and Fe2Et (τ5 = 0.28). Upon in situ activation with either MAO or MMAO cocatalysts, all iron complexes displayed distinguished polymerization performance, especially in terms of thermo-stability. In particular, the less hindered Fe2Me exhibited high activity: 20.4 × 106 g mol−1 h−1 at 70 °C, 1.5 × 106 g mol−1 h−1 at 110 °C, and 0.6 × 106 g mol−1 h−1 at 120 °C. Whereas, the sterically more hindered Fe2iPr proved to be more productive in generating high molecular weight polyethylene (Mw up to 410.7 kg mol−1 at 70 °C). Moreover, by adjusting the reaction temperature and ligand structure, the chain termination reaction could be modulated from a high proportion of vinyl-terminated polyethylene to saturated polyethylene rich product [CH2CH(CH2)nCH3/CH3(CH2)nCH3 = 0.7/0.3–0.39/0.61], as confirmed by high-temperature 1H/13C NMR spectra. Low molecular weight vinyl-terminated polyethylenes are of significant importance in the synthesis of functional polymers and can serve as valuable additives in lubricants.

Recyclable Alloy Nanocatalyst-Mediated Photo-Controlled Synthesis of Functional Polymers for Toxic Metal and Dye Removal

Recyclable Alloy Nanocatalyst-Mediated Photo-Controlled Synthesis of Functional Polymers for Toxic Metal and Dye Removal

Polysulfide-ene polymerization of bisacrylamides and bismaleimides toward sulphur-rich polymers

Given the ever-increasing importance of developing more sustainable solutions for the fabrication and engineering of polymeric materials, alternative building blocks to the petroleum-derived chemicals are gaining growing interest. In addition to its natural abundance, elemental sulfur is produced industrially in vast quantities which is primarily obtained as a side product from oil refineries and gas purification plants. Thus, elemental sulfur has been prospected as a sustainable resource for the fabrication of structurally diverse polymers. In this study an efficient methodology to obtain sulfur-rich polymers from elemental sulfur-derived polysulfide salts is reported. Polysulfide-ene step growth polymerization of bisacrylamide and bismaleimide-based monomers with bifunctional disodium pentasulfide (Na2S5) generated structurally diverse polyamide and polyimide copolymers incorporating polysulfide chains on the polymer backbones. Copolymers up to 31.8 kDa molecular weight (Mn) and 94% monomerconversions were efficiently obtained under ambient temperature conditions and without the need of any metal or organo-catalyst. By choosing various bifunctional ene monomers, structurally diverse and tailorable linear copolymers were obtained. The methodology was also extended to the fabrication of sulfur-rich crosslinked polymers by employing a multifunctional thiolate-based crosslinker. As a potential application, fabricated crosslinked polymers were employed as adsorbents to remove toxic mercury ions from water. The reported synthetic strategy demonstrated the efficiency of polysulfide-ene reaction to synthesize sulfur-rich polyamide and polyimide polymers and could broaden the available polymerization reaction tools that employelemental sulfur-derived polysulfide salts in functional polymer synthesis.

Current Trends in the Synthesis of Inorganic and Organoelement Phosphorus- and Sulfur-Containing Polymers. A Review

An analysis of literature data on the set of reactions for the production of macromolecules with a high content of phosphorus and sulfur has been carried out, and basic approaches that allow the introduction of these elements into the composition of polymers and polymeric materials have been considered in compliance with the fundamental principles of green chemistry. Methods for synthesis of functional polymers under mild conditions that require minimal energy input from external sources, which can become new growth points for green industrial technologies, are considered. Particular attention focuses on the synthesis of polyphosphazenes and polyphosphoesters for biomedical purposes, as well as on the inverse vulcanization reaction to give polymers used in sorption wastewater treatment, the creation of current sources, and IR optics.

Mechanochemical Synthesis of Stimuli Responsive Microgels.

Mechanochemical approaches are widely used for the efficient, solvent-free synthesis of organic molecules, however their applicability to the synthesis of functional polymers has remained underexplored. Herein, we demonstrate for the first time that mechanochemically triggered free-radical polymerization allows solvent- and initiator-free syntheses of structurally and morphologically well-defined complex functional macromolecular architectures, namely stimuliresponsive microgels. The developed mechanochemical polymerization approach is applicable to a variety of monomers and allows synthesizing microgels with tunable chemical structure, variable size, controlled number of crosslinks and reactive functional end-groups.

Mechanochemical Synthesis of Stimuli Responsive Microgels

AbstractMechanochemical approaches are widely used for the efficient, solvent‐free synthesis of organic molecules, however their applicability to the synthesis of functional polymers has remained underexplored. Herein, we demonstrate for the first time that mechanochemically triggered free‐radical polymerization allows solvent‐ and initiator‐free syntheses of structurally and morphologically well‐defined complex functional macromolecular architectures, namely stimuliresponsive microgels. The developed mechanochemical polymerization approach is applicable to a variety of monomers and allows synthesizing microgels with tunable chemical structure, variable size, controlled number of crosslinks and reactive functional end‐groups.

Titelbild: Mechanochemical Synthesis of Stimuli Responsive Microgels (Angew. Chem. 34/2023)

Mechanochemical approaches are widely used for the efficient, solvent-free synthesis of organic molecules, however their applicability to the synthesis of functional polymers has remained underexplored. In their Research Article (e202305783), Carsten Bolm, Andrij Pich, and co-workers developed a free-radical polymerization approach to mechanochemically synthesize structurally and morphologically well-defined complex functional macromolecular architectures, stimuli-responsive microgels, in the conditions of solvent- and initiator-free.

Cover Picture: Mechanochemical Synthesis of Stimuli Responsive Microgels (Angew. Chem. Int. Ed. 34/2023)

Mechanochemical approaches are widely used for the efficient, solvent-free synthesis of organic molecules, however their applicability to the synthesis of functional polymers has remained underexplored. In their Research Article (e202305783), Carsten Bolm, Andrij Pich, and co-workers developed a free-radical polymerization approach to mechanochemically synthesize structurally and morphologically well-defined complex functional macromolecular architectures, stimuli-responsive microgels, in the conditions of solvent- and initiator-free.

Methods of controlled radical polymerization in the synthesis of functional polymers and macromolecular structures

Methods of controlled radical polymerization in the synthesis of functional polymers and macromolecular structures

Precise control of conjugated polymer synthesis from step-growth polymerization to iterative synthesis

Conjugated polymers with excellent optoelectronic properties, easy processability, and flexible physical properties are versatile in various applications. In recent years, the precise synthesis of conjugated polymers has attracted much attention due to the close relationship between structure and property. From the perspective of the polymerization mechanism, the synthetic methods of conjugated polymers can be classified into step-growth polymerization, chain-growth polymerization, and iterative synthesis. From step-growth polymerization to iterative synthesis, polymer synthesis becomes more controllable. In this review, we introduce these three synthetic approaches to prepare conjugated polymers with controllable structures based on transition metal-catalyzed cross-coupling reactions and further reveal the control over chemical structures, including length, regioregularity, sequence, and topology. The precise control over the synthesis of conjugated polymer is of great significance for the synthesis of functional polymer with a specific structure, which paves a way for fabricating high-performance devices.

Emerging Bio-Based Polymers from Lab to Market: Current Strategies, Market Dynamics and Research Trends

Due to the rising worldwide demand for green chemicals, the bio-based polymer market is anticipated to expand substantially in the future. The synthesis of functional polymers has been a burgeoning area of research for decades. The primary driving force behind the development of bio-based polymers has been their compostability and biodegradability, which are critical given the public concern about waste. Significant advancements in the method for refining biomass raw materials towards the creation of bio-based construction materials and products are driving this rise. Bio-based polymers with this chemical structure are more flexible and adaptive, which allows them to attain their intended characteristics and functionalities. In commercial applications and healthcare and biotechnology, where completely manufactured, naturally occurring biomolecules are utilized and such polymers have the greatest impact. At the same time, limitations in polymer architectural control, biostability, and structural dynamics hinder the creation of biocompatible and functionally varied polymers. From this standpoint, the importance of functional biosynthetic polymers in the future years is highlighted, as well as new methods for addressing the aforementioned challenges. The article comprehensively highlighted the current strategies, market dynamics, and research trends of emerging Bio-Based Polymers. In addition, the most recent scientific breakthroughs in bio-based polymers are discussed.

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.

Polymer Materials Synthesized through Cell-Mediated Polymerization Strategies for Regulation of Biological Functions

ConspectusAs essential components of living organisms, biomacromolecules construct cell scaffolds and regulate cell activities and biological functions through chemical transformations in biological systems. Inspired by the functional evolution in the formation of natural structures, in situ polymerization methods have been developed to create functional synthetic macromolecules inside or on the surface of living cells. Given the diversity of cell species and the complexity of biological pathways, selected strategies can be employed to control the synthesis of functional polymers that utilize the dynamic cellular microenvironment.In this Account, we summarize recent work in the field of designing cell-mediated in situ polymerization methods, with which we demonstrate their application prospects including tumor cell labeling and treatment, microbial photosynthetic efficiency regulation, and hydrogel generation. The purpose of these efforts is to design polymerization reactions in response to endogenous or exogenous stimuli and to describe the underlying response mechanisms. By reasonable design of molecular structures, in situ synthesized polymers in the cell microenvironment implement regulation of biological functions. For example, using specific redox activity combined with light irradiation, bacteria can mediate the generation of functional polymers as the encapsulating matrix or with antibacterial effects. Conjugated polymers synthesized on the microalgae surface expanded the spectral absorption and improved photosynthetic efficiency. Meanwhile, characteristics of the cellular microenvironment could initiate various polymerization reactions inside living cells, including oxidative thiol cross-linking, condensation polymerization, and free radical polymerization. These reactions can be selectively conducted with reactive species generated in tumor cells, and the resulting polymers showed prolonged retention inside cells for modulating cell behaviors. Further development of cell-mediated polymerization strategies would provide an innovative platform for research and applications of multifunctional biomaterials and engineered biohybrid systems.

Polymers with Pendant Water‐Soluble Tetrafluorobenzene Sulfonic Acid Activated Esters: Synthesis, Stability, and Use for Glycopolymers in Water

Front Cover: In article number 2200072, Tomonari Tanaka and co-workers synthesize a novel monomer and polymer bearing water-soluble activated ester groups, tetrafluorobenzene sulfonic acid esters, with a pentandiyl linker. These are stable and can be used for synthesizing glycopolymers in water. Synthesis of functional polymers in water are further developed.

New Approaches to Atom Transfer Radical Polymerization and Their Realization in the Synthesis of Functional Polymers and Hybrid Macromolecular Structures

New Approaches to Atom Transfer Radical Polymerization and Their Realization in the Synthesis of Functional Polymers and Hybrid Macromolecular Structures

Diversity-Oriented Synthesis of Functional Polymers with Multisubstituted Small Heterocycles by Facile Stereoselective Multicomponent Polymerizations

Diversity-Oriented Synthesis of Functional Polymers with Multisubstituted Small Heterocycles by Facile Stereoselective Multicomponent Polymerizations

Multicomponent approach for the synthesis of functional copolymers via tandem polycondensations of isatoic anhydride, bisaldehydes and bisprimary amines in trifluoroethanol

A novel multicomponent polymerization strategy based on the tandem reactions of isatoic anhydride with bisaldehyde and bisamine monomers under mild metal catalyst-free conditions was developed. • Multicomponent synthesis of poly(dihydroquinazolinone)s was achieved. • MCP utilizes isatoic anhydride, bisaldehyde and bisamine monomers. • Obtained polymers show pH-dependent phase changes. A novel multicomponent polymerization (MCP) strategy based on tandem reactions of isatoic anhydride with bisprimary amine and bisaldehyde monomers under mild metal catalyst-free conditions was developed, leading to tailor-made copolymers carrying dihydroquinazolinone groups in the main chains. Trifluoroethanol was employed as a solvent during polymerization due to its high solvating ability of growing chains as well as its strong Brønsted acid character that allows high activation of tandem polycondensations. Functional copolymers in the range from 8.5 kDa to 23.2 kDa molecular weights (M n ) were synthesized with moderately high monomer conversions. By simple alteration of bisaldehyde and bisamine monomers, a structurally diverse functional copolymer library was obtained. The polycondensation mechanism proceeds on the liberation of CO 2 and H 2 O byproducts and together with the solvent reusability, this multicomponent polymerization allows a green approach to functional polymer synthesis. The obtained results demonstrated that the corresponding cationic polymers display post-polymerization modification feature and pH-dependent phase changes that suggest their potential use in various material applications.

Synthesis and properties of functional polymer for heavy oil viscosity reduction

To address chromatographic separation issues encountered with surfactant-polymer composite systems, a functional polymer (PAA-NA) was synthesized from acrylamide, 2-acrylamido-2-methylpropane sulfonic acid and two functional monomers, namely C14-C22 fatty alcohol polyoxyethylene ether acrylate (AEO15AA) and N-dodecylprop-2-enamide (C12AM), to realize heavy oil emulsification and viscosity reduction under reservoir conditions. Proton nuclear magnetic resonance analysis (1HNMR) verified the synthesis of PAANA. Relevant properties, including thickening performance, salt-tolerance, interfacial activity, and interfacial elasticity as well as heavy oil viscosity reduction capabilities of PAANA, PAA-N comprising C12AM, and PAA-A comprising AEO15AA were studied systematically. PAA-NA exhibited a superior viscosity reduction performance compared to that of PAA-A and PAA-N owing to the synergistic effect of the two functional monomers: (1) the higher the degree of hydrophobic association, the stronger the spatial network structure, resulting in improved thickening performance, interfacial elasticity, and shear resistance. Meanwhile, a tighter interfacial adsorption layer was formed at the oil-water interface, reducing interfacial tension. (2) heavy oil viscosity reduction rates by PAA-NA (87.0%–90.6%) were higher than those achieved with PAA-A (55.7%–76.0%), while PAA-N was unable to reduce the viscosity. The oil-water ratio range that favors the formation of O/W emulsions was wider for PAA-NA (less than 7:3) than for PAA-A (less than 4:6). The synthesis of functional polymer PAA-NA as a viscosity reducer bears theoretical significance for the enhancement of heavy oil recovery

Recent progress in the applications of amino–yne click chemistry

This mini-review summarizes the recent research studies on the application of the amino–yne click reaction in surface immobilization, construction of drug delivery systems, preparation of hydrogel materials and synthesis of functional polymers.

Catalyst‐Free Four‐Component Polymerization of Propiolic Acids, Benzylamines, Organoboronic Acids, and Formaldehyde toward Functional Poly(propargylamine)s

Multicomponent polymerizations (MCPs) are a group of fascinating polymer synthesis approaches that are developed rapidly in the recent decade. As a popular alkyne-based MCP, the A3 -polycouplings of alkynes, aldehydes, and amines are developed for the synthesis of poly(propargylamine)s under the catalysis of metal catalysts. In this work, through the design of carboxylic acid group-activated alkyne monomers, a catalyst-free, four-component polymerization of propiolic acids, benzylamines, organoboronic acids, and formaldehyde is reported under mild condition at 45°C in dichloroethane. This four-component polymerization is applicable to different monomer structures, which can afford seven poly(propargylamine)s with up to 94% yields and molecular weights of up to 13 900gmol-1 . Moreover, the poly(propargylamine)s demonstrate good solubility and processibility, high thermal stability and light refractivity, unique photophysical property, and so on. The simple monomers, mild condition, low cost, high efficiency, and procedure simplicity of this catalyst-free four-component polymerization demonstrates an elegant example of functional polymer synthesis.