Insights into Mechanochemical Solid-State Ball-Milling Reaction: Monitoring Transition from Heterogeneous to Homogeneous Conditions.

As mechanochemical synthesis has advanced significantly, there has been intense interest in understanding the underlying mechanisms of these reactions. Given that many mechanochemical processes are conducted in the solid-state without solvation yet sometimes yield faster reactions than those in solution, we sought to address the following question: Are mechanochemical reactions homo- or heterogeneous? To investigate, we employed a model system involving the mixing and copolymerization of l-lactide (LLA) and d-lactide (DLA), monitored through powder X-ray diffraction (PXRD), nuclear magnetic resonance, and differential scanning calorimetry. and PXRD analyses of the mixture of LLA and DLA showed that vibratory ball milling rapidly transformed the initially heterogeneous lactide mixture into a homogeneous phase within one min due to collisions between the balls and the jar.

C-H Functionalization of Poly(ethylene oxide) - Embracing Functionality, Degradability, and Molecular Delivery.

This study presents an organocatalytic C-H functionalization approach for postpolymerization modification (PPM) of poly(ethylene oxide) (PEO). Most of PEO PPM is previously processed at the end hydroxy group, but recent advances in C-H functionalization open a way to modify the backbone position. Structurally diverse carboxylic acids are attached to PEO through a cascade process of radical generation by peroxide and oxidation to oxocarbenium by tertiary butylammonium iodide.

Physical Adsorption of Polyacrylic Acid on Boron Nitride Nanotube Surface and Enhanced Thermal Conductivity of Poly(vinyl alcohol) Composites.

To fully tap into the potential of boron nitride nanotubes (BNNTs), addressing their inherent insolubility was imperative. In this study, a water-soluble polymer, poly(acrylic acid) (PAA), was employed as a surface-active reagent, using an accessible and scalable approach. The physical properties and structure of PAA-BNNT were meticulously confirmed through valuable characterization techniques, encompassing X-ray diffraction, scanning electron microscopy, Fourier-transform infrared, X-ray photoelectron spectroscopy, and thermogravimetric analysis.

Facile covalent functionalization of boron nitride nanotubes coupling reaction.

A broad range of functionalized boron nitride nanotubes has been synthesized using a facile method based on the coupling reaction between BNNT and arenediazonium tetrafluoroborate derivatives. The formation of covalent bonds between nanotubes and organic moieties results in homogeneous dispersions in organic solvents, such as ,'-dimethylformamide, acetone, isopropanol, and tetrahydrofuran. Digital images demonstrated improved and stabilized dispersions lasting for several days, while TEM analysis indicated no breakdown of nanotubes due to the mild reaction conditions employed.

Mechanochemical ring-opening metathesis polymerization: development, scope, and mechano-exclusive polymer synthesis.

Ruthenium-alkylidene initiated ring-opening metathesis polymerization has been realized under solid-state conditions by employing a mechanochemical ball milling method. This method promotes greenness and broadens the scope to include mechano-exclusive products. The carbene- and pyridine-based Grubbs 3-generation complex outperformed other catalysts and maintained similar mechanistic features of solution-phase reactions.

Mechanochemical solid-state vinyl polymerization with anionic initiator.

Mechanochemistry has been extended to various polymer syntheses to achieve efficiency, greenness, and new products. However, many fundamental polymerization reactions have not been explored, although anionic polymerization of vinyl compounds has been pursued under mechanochemical conditions. Two solid monomers, 4-biphenyl methacrylate and 4-vinyl biphenyl, representing methacrylate and styrenic classes, respectively, were reacted with secondary butyl lithium under high-speed ball-milling.

The mechanochemical synthesis of polymers.

Mechanochemistry - the utilization of mechanical forces to induce chemical reactions - is a rarely considered tool for polymer synthesis. It offers numerous advantages such as reduced solvent consumption, accessibility of novel structures, and the avoidance of problems posed by low monomer solubility and fast precipitation. Consequently, the development of new high-performance materials based on mechanochemically synthesised polymers has drawn much interest, particularly from the perspective of green chemistry.

Mechanochemical Iridium(III)-Catalyzed B-Amidation of -Carboranes with Dioxazolones.

Mechanochemistry was successfully applied to the functionalization of carboranes. The mechanochemical iridium(III)-catalyzed regioselective B(3)- and B(4)-amidation of unsubstituted -carboranes with dioxazolones was developed. In addition, the mechanochemical iridium(III)-catalyzed regioselective B(4)-amidation of substituted -carboranes was demonstrated.

Sequential Post-Polymerization Modification of Aldehyde Polymers to Ketone and Oxime Polymers.

A new sequential post-polymerization modification route has been developed for the synthesis of multifunctional polymers from a simple aldehyde polymer. In the first modification step, a template polymer derived from the radical polymerization of 4-vinyl benzaldehyde undergoes Rh-catalyzed hydroacylation with alkenes to furnish a group of ketone polymers. In the second modification step, Schiff base formation with alkoxy ammonium salts introduces a second group-an oxime functionality.

Solvent-Free Mechanochemical Post-Polymerization Modification of Ionic Polymers.

Despite their superior stability and facile handling, ionic polymers have limited solubility in most organic solvents, restricting the range of substrates and reaction conditions to which they can be applied. To overcome this solubility issue, the present study presents a solvent-free mechanochemical reaction. Specifically, a post-polymerization modification of ammonium-functionalized polyether was demonstrated using a solvent-free vibrational ball-milling technique.

Chemical Upcycling of Waste Poly(bisphenol A carbonate) to 1,4,2-Dioxazol-5-ones and One-Pot C-H Amidation.

Chemical upcycling of poly(bisphenol A carbonate) (PC) was achieved in this study with hydroxamic acid nucleophiles, giving rise to synthetically valuable 1,4,2-dioxazol-5-ones and bisphenol A. Using 1,5,7-triazabicyclo[4.4.

Molecular Weight Dependent Morphological Transitions of Bottlebrush Block Copolymer Particles: Experiments and Simulations.

The molecular weights and chain rigidities of block copolymers can strongly influence their self-assembly behavior, particularly when the block copolymers are under confinement. We investigate the self-assembly of bottlebrush block copolymers (BBCPs) confined in evaporative emulsions with varying molecular weights. A series of symmetric BBCPs, where polystyrene (PS) and polylactide (PLA) side-chains are grafted onto a polynorbornene (PNB) backbone, are synthesized with varying degrees of polymerization of the PNB () ranging from 100 to 300.

Synthesis of Polypropylene via Catalytic Deoxygenation of Poly(methyl acrylate).

We propose the defunctionalization of vinyl polymers as a strategy to access previously inaccessible polyolefin materials. By utilizing B(CF)-catalyzed deoxygenation in the presence of silane, we demonstrate that eliminating the pendent ester in poly(methyl acrylate) effectively leaves a linear hydrocarbon polymer with methyl pendants, which is polypropylene. We further show that a polypropylene--polystyrene diblock copolymer and a polystyrene--polypropylene--polystyrene triblock copolymer can be successfully derived from the poly(methyl acrylate)-containing block polymer precursors and exhibit quite distinct materials properties due to their chemical transformation.

Mechanochemical synthesis of poly(trimethylene carbonate)s: an example of rate acceleration.

Mechanochemical polymerization is a rapidly growing area and a number of polymeric materials can now be obtained through green mechanochemical synthesis. In addition to the general merits of mechanochemistry, such as being solvent-free and resulting in high conversions, we herein explore rate acceleration under ball-milling conditions while the conventional solution-state synthesis suffer from low reactivity. The solvent-free mechanochemical polymerization of trimethylene carbonate using the organocatalysts 1,8-diazabicyclo[5.

Diphenyl Carbonate: A Highly Reactive and Green Carbonyl Source for the Synthesis of Cyclic Carbonates.

A practical, safe, and highly efficient carbonylation system involving a diphenyl carbonate, an organocatalyst, and various diols is presented herein and produces highly valuable cyclic carbonates. In reactions with a wide range of diols, diphenyl carbonate was activated by bicyclic guanidine 1,5,7-triazabicyclo[4.4.

Mechanochemical Post-Polymerization Modification: Solvent-Free Solid-State Synthesis of Functional Polymers.

Mechanochemical postpolymerization modification is reported herein. The fast and efficient synthesis of a library of macromolecules with functional diversity and structural uniformity was realized without a solvent by means of a high speed ball-milling technique. A series of polymers prepared from 4-vinylbenzaldehyde (4-VBA) underwent solid-state Schiff base formations with a series of amines and amine derivatives.

Mechanochemical Ring-Opening Polymerization of Lactide: Liquid-Assisted Grinding for the Green Synthesis of Poly(lactic acid) with High Molecular Weight.

Mechanochemical polymerization of lactide is carried out by using ball milling. Mechanical energy from collisions between the balls and the vessel efficiently promotes an organic-base-mediated metal- and solvent-free solid-state polymerization. Investigation of the parameters of the ball-milling synthesis revealed that the degree of lactide ring-opening polymerization could be modulated by the ball-milling time, vibration frequency, mass of the ball media, and liquid-assisted grinding.

Metal-Free Hydrosilylation Polymerization by Borane Catalyst.

The first example of metal-free hydrosilylation polymerization between dienes and disilanes is developed by using a borane catalyst, B(C6F5)3 to replace precious transition-metal-based systems. Under the easy-to-handle and mild conditions, a step-growth polymerization of two readily available diene and disilane units was achieved with high degrees of polymerization. Various combinations of dienes and disilanes produced polycarbosilanes with a broad range of structures and properties.

Mechanistic studies on the Rh(III)-mediated amido transfer process leading to robust C-H amination with a new type of amidating reagent.

Mechanistic investigations on the Cp*Rh(III)-catalyzed direct C-H amination reaction led us to reveal the new utility of 1,4,2-dioxazol-5-one and its derivatives as highly efficient amino sources. Stepwise analysis on the C-N bond-forming process showed that competitive binding of rhodium metal center to amidating reagent or substrate is closely related to the reaction efficiency. In this line, 1,4,2-dioxazol-5-ones were observed to have a strong affinity to the cationic Rh(III) giving rise to dramatically improved amidation efficiency when compared to azides.