Mechanochemical Polymerization Research Articles

Anionic ring-opening polymerization of functional epoxide monomers in the solid state

Despite recent advancements in mechanochemical polymerization, understanding the unique mechanochemical reactivity during the ball milling polymerization process still requires extensive investigations. Herein, solid-state anionic ring-opening polymerization is used to synthesize polyethers from various functional epoxide monomers. The critical parameters of the monomers are investigated to elucidate the unique reactivity of ball milling polymerization. The controllable syntheses of the desired polyethers are characterized via NMR, GPC, and MALDI-ToF analyses. Interestingly, bulky monomers exhibit faster conversions in the solid-state in clear contrast to that observed for solution polymerization. Particularly, a close linear correlation is observed between the conversion of the ball milling polymerization and melting point of the functional epoxide monomers, indicating melting point as a critical predictor of mechanochemical polymerization reactivity. This study provides insights into the efficient design and understanding of mechanochemical polymerization.

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.

TM-Free and TM-Catalyzed Mechanosynthesis of Functional Polymers.

Mechanochemically induced methods are commonly used for the depolymerization of polymers, including plastic and agricultural wastes. So far, these methods have rarely been used for polymer synthesis. Compared to conventional polymerization in solutions, mechanochemical polymerization offers numerous advantages such as less or no solvent consumption, the accessibility of novel structures, the inclusion of co-polymers and post-modified polymers, and, most importantly, the avoidance of problems posed by low monomer/oligomer solubility and fast precipitation during polymerization. Consequently, the development of new functional polymers and materials, including those based on mechanochemically synthesized polymers, has drawn much interest, particularly from the perspective of green chemistry. In this review, we tried to highlight the most representative examples of transition-metal (TM)-free and TM-catalyzed mechanosynthesis of some functional polymers, such as semiconductive polymers, porous polymeric materials, sensory materials, materials for photovoltaics, etc.

Diverse Methods to Nanomanufacture Colloidal Dispersions of Polyaniline without Templates

Different methods which could be used to produce colloidal dispersions of polyaniline (PANI) nano-objects without templates are described. While the methods are non-deterministic, different nano-objects (nanospheres, nanofibers, nanobelts, nanorice, nanotubes, nanorods, nanodisks, etc.) can be produced. Those most used are: (i) solution polymerization with steric stabilizers (SPS) to produce nanospheres, (ii) interfacial polymerization (IP) to produce nanofibers and (iii) solution polymerization in the presence of additives (SPA) to produce nanotubes. Oxidation of aniline in aqueous solution could produce nanotubes, nanofibers and other shapes by controlling mass transport/concentration of reactants, pH, and the presence of oligomers/additives. The different models proposed to explain the formation of various nano-objects are discussed. Mechanochemical polymerization (MCP) could produce nanofibers or nanospheres by controlling the aniline/oxidant ratio. PANI nanospheres of tunable sizes can also be produced by nanoprecipitation (NPT) of preformed PANI from its solutions using an antisolvent. The geometrical constraints to the small nano-objects made of high-molecular-weight rigid polymers are described. The conditions to produce nanostructures also affect the intrinsic properties of PANI (conductivity, crystallinity, and electroactivity). Selected technological applications of PANI nano-objects manufactured as colloidal dispersions without templates are discussed. Based on the reviewed work and models, future lines of work are proposed.

Mechanochemical Synthesis of Polyanilines and Their Nanocomposites: A Critical Review.

The mechanochemical synthesis of polyanilines (PANIs), made by oxidative polymerization of anilines, is reviewed. First, previous knowledge of the polymerization reaction in solution is discussed to understand the effect of different parameters: oxidant/monomer ratio, added acid, oxidant, temperature and water content on the properties of the conducting polymers (molecular weight, degradation, doping/oxidation level, conductivity, and nanostructure). The work on mechanochemical polymerization (MCP) of anilines is analyzed in view of previous data in solution, and published data are critically reconsidered to clarify the interpretation of experimental results. A key factor is the production of acids during polymerization, which is often overlooked. The production of gaseous HCl during MCP of aniline hydrochloride is experimentally observed. Since some experiments involves the addition of small amounts of water, the kinetics and heat balance of the reaction with concentrated solutions were simulated. A simple experiment shows fast (<2 min) heating of the reaction mixture to the boiling point of water and temperature increments are observed during MCP in a mortar. The form and sizes of PANI nanostructures made by MCP or solution are compared. The extensive work on the production of nanocomposites by MCP of anilines together with different nanomaterials (porous clays, graphene, carbon nanotubes, metal, and oxide nanoparticles) is also described.

The mechanochemical Friedel‐Crafts polymerization as a solvent‐free cross‐linking approach toward microporous polymers

AbstractHerein we report the mechanochemical Friedel‐Crafts alkylation of 1,3,5‐triphenylbenzene (TPB) with two organochloride cross‐linking agents, dichloromethane (DCM) and chloroform (CHCl3), respectively. During a thorough milling parameter evaluation, the DCM‐linked polymers were found to be flexible and extremely sensitive toward parameter changes, which even enables the synthesis of a polymer with a SSABET of 1670 m2/g, on par with the solution‐based reference. Contrary, CHCl3‐linked polymers are exhibiting a rigid structure, with a high porosity that is widely unaffected by parameter changes. As a result, a polymer with a SSABET of 1280 m2/g could be generated in as little as 30 minutes, outperforming the reported literature analogue in terms of synthesis time and SSABET. To underline the environmental benefits of our fast and solvent‐free synthesis approach, the green metrics are discussed, revealing an enhancement of the mass intensity, mass productivity and the E‐factor, as well as of synthesis time and the work‐up in comparison to the classical synthesis. Therefore, the mechanochemical polymerization is presented as a versatile tool, enabling the generation of highly porous polymers within short reaction times, with a minimal use of chlorinated cross‐linker and with the possibility of a post polymerization modification.

Preparation of the Silica Filler by Mechanochemical Polymerization in Water

Preparation of the Silica Filler by Mechanochemical Polymerization in Water

Liquid Metal–Mediated Mechanochemical Polymerization

Mechanically controlled polymerization that employs the mechanical energy to fabricate novel synthetic materials has attracted considerable interest. However, only a few examples have been achieved so far, owing to the limited choices of materials and strategies. Herein, a versatile, liquid metal (LM)-mediated mechanochemical polymerization method (LMMMP) is developed for the air-compatible, robust preparation of polymers in an aqueous solution. This method involves the simultaneous disruption of bulk LMs into micro- and nanodroplets and the combination of monomers into polymers during ultrasonic irradiation. The pristine and reactive LM surface continuously generated by ultrasound endows this polymerization method with excellent oxygen tolerance, high reaction rate, and the ability to produce polymers with high molecular weight from a wide variety of water-soluble monomers. Besides, LM droplets are readily reclaimed and reused for polymerization. The authors envision that the LMMMP promotes the utilization of mechanical energy for the synthesis of functional polymers, constitutes a novel fabrication approach for polymer-LM nanocomposites, and provides new insight into the design of LM-based platforms for polymerization.

Liquid Metal-Mediated Mechanochemical Polymerization.

Mechanically controlled polymerization that employs the mechanical energy to fabricate novel synthetic materials has attracted considerable interest. However, only a few examples have been achieved so far, owing to the limited choices of materials and strategies. Herein, a versatile, liquid metal (LM)-mediated mechanochemical polymerization method (LMMMP) is developed for the air-compatible, robust preparation of polymers in an aqueous solution. This method involves the simultaneous disruption of bulk LMs into micro- and nanodroplets and the combination of monomers into polymers during ultrasonic irradiation. The pristine and reactive LM surface continuously generated by ultrasound endows this polymerization method with excellent oxygen tolerance, high reaction rate, and the ability to produce polymers with high molecular weight from a wide variety of water-soluble monomers. Besides, LM droplets are readily reclaimed and reused for polymerization. The authors envision that the LMMMP promotes the utilization of mechanical energy for the synthesis of functional polymers, constitutes a novel fabrication approach for polymer-LM nanocomposites, and provides new insight into the design of LM-based platforms for polymerization.

Solvent-free mechanochemical polymerization of urea-succinic acid and urea-succinic acid-glycerol mixtures

Abstract Copolymers of urea and succinic acid (U/SA) and urea, succinic acid and glycerol (U/SA/GLY) were prepared through green mechanochemical reactions, without the use of solvents. A planetary ball mill was used for the polymerization operation and the effects of some of the polymerization conditions were investigated. The obtained samples were analyzed by Fourier Transform Infrared Spectroscopy (FTIR/ATR), Electrospray ionization mass spectrometry (IES-EM), Matrix- Assisted Laser Desorption Ionization Process (MALDI TOF), Nuclear Magnetic Resonance (1H NMR and 13C NMR), Thermal Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC), in order to study the structural, chemical and thermal properties of the obtained products. The results confirmed the occurrence of mechanochemical polymerizations of urea and succinic acid and of urea, succinic acid and glycerol. A relatively high yield of 83% (U/SA) and 75% (U/SA/GLY) and maximum degradation temperature of 290 °C were achieved using this novel solid copolymerization method. The method proved to be versatile, convenient and suitable for green and sustainable production of polymer materials, in particular for the coating of urea granules.

Mechanochemical synthesis of hyper-crosslinked polymers: influences on their pore structure and adsorption behaviour for organic vapors.

This study elucidates a mechanochemical polymerization reaction towards a hyper-crosslinked polymer as an alternative to conventional solvent-based procedures. The swift and solvent-free Friedel–Crafts alkylation reaction yields a porous polymer with surface areas of up to 1720 m2g−1 and pore volumes of up to 1.55 cm3g−1. The application of LAG (liquid-assisted grinding) revealed a profound impact of the liquid´s boiling point on the textural properties of the obtained polymer materials. Finally, the materials are characterized by vapour sorption experiments with benzene and cyclohexane.

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[5.4.0]undec-7-ene (DBU) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) are examined herein. The polymerizations under ball-milling conditions exhibited significant rate enhancements compared to polymerizations in solution. A number of milling parameters were evaluated for the ball-milling polymerization. Temperature increases due to ball collisions and exothermic energy output did not affect the polymerization rate significantly and the initial mixing speed was important for chain-length control. Liquid-assisted grinding was applied for the synthesis of high molecular weight polymers, but it failed to protect the polymer chain from mechanical degradation.

Tailoring the porosity of a mesoporous carbon by a solvent-free mechanochemical approach

The synthesis of mesoporous carbons with well-defined and tailored pores conventionally involves the use of solvents and proceeds via multiple synthesis steps such as template synthesis and precursor infiltration. In this work, a solvent-free mechanochemical polymerization is used to derive mesoporous carbons with narrow pore size distributions and specific surface areas of up to 1660 m2 g−1. The size of the mesopores can be tailored by simply adjusting milling parameters like the milling speed. Finally, the carbons have been applied as supercapacitors through a new approach - the ‘in situ electrolyte’ concept. This holistic concept does not treat the accumulating by-products of the carbon synthesis as waste, but rather utilizes them directly as electrolyte salts. With this, washing steps are circumvented and the use of any solvent becomes obsolete.

Surface Chemistry Dependence of Mechanochemical Reaction of Adsorbed Molecules-An Experimental Study on Tribopolymerization of α-Pinene on Metal, Metal Oxide, and Carbon Surfaces.

Mechanochemical reactions between adsorbate molecules sheared at tribological interfaces can induce association of adsorbed molecules, forming oligomeric and polymeric products often called tribopolymers). This study revealed the role or effect of surface chemistry of the solid substrate in mechanochemical polymerization reactions. As a model reactant, α-pinene was chosen because it was known to readily form tribopolymers at the sliding interface of stainless steel under vapor-phase lubrication conditions. Eight different substrate materials were tested-palladium, nickel, copper, stainless steel, gold, silicon oxide, aluminum oxide, and diamond-like carbon (DLC). All metal substrates and DLC were initially covered with surface oxide species formed naturally in air or during the oxidative sample cleaning. It was found that the tribopolymerization yield of α-pinene is much higher on the substrates that can chemisorb α-pinene, compared to the ones on which only physisorption occurs. From the load dependence of the tribopolymerization yield, it was found that the surfaces capable of chemisorption give a smaller critical activation volume for the mechanochemical reaction, compared to the ones capable of physisorption only. On the basis of these observations and infrared spectroscopy analyses of the adsorbed molecules and the produced polymers, it was concluded that the mechanochemical reaction mechanisms might be different between chemically reactive and inert surfaces and that the chemical reactivity of the substrate surface greatly influences the tribochemical polymerization reactions of adsorbed molecules.

High-Pressure Chemistry and the Mechanochemical Polymerization of [5]-Cyclo-p-phenylene.

Evidence for the surprising formation of polymeric phases under high pressure for conjugated nanohoop molecules was found. This paper represents one of the unique cases, in which the molecular-level effects of pressure in crystalline organic solids is addressed, and provides a general approach based on vibrational Raman spectroscopy combining experiments and computations. In particular, we studied the structural and supramolecular chemistry of the cyclic conjugated nanohoop molecule [5]cyclo-para-phenylene ([5]CPP) under high pressures up to 10 GPa experimentally and up to 20 GPa computationally. The theoretical modeling for periodic crystals predicts good agreements with the experimentally obtained Raman spectra in the molecular phase. In addition, we have discovered two stable polymeric phases that arise in the simulation. The critical pressures in the simulation are too high, but the formation of polymeric phases at high pressures provides a natural explanation for the observed irreversibility of the Raman spectra upon pressure release between 6 and 7 GPa. The geometric parameters show a deformation toward quinonoid structures at high pressures accompanied by other deformations of the [5]CPP nanohoops. The quinonoidization of the benzene rings is linked to the systematic change of the bond length alternation as a function of the pressure, providing a qualitative interpretation of the observed spectral shifts of the molecular phase.

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. Liquid-assisted grinding was found to be an especially important factor for achieving a high degree of mechanochemical polymerization. Although polymer-chain scission from the strong collision energy prevented mechanical-force-driven high-molecular-weight polymer synthesis, the addition of only a small amount of liquid enabled sufficient energy dissipation and poly(lactic acid) was thereby obtained with a molecular weight of over 1×105 g mol-1 .

アルミナ粉砕によるMMAのメカノケミカル重合反応に及ぼす溶媒の影響

Mechanochemical polymerization of methyl methacrylate (MMA) monomer was carried out by grinding alumina powder that had high thermal conductivity. A planetary ball mill with high grinding ability was used because alumina has high hardness. The experiments were conducted using different monomer concentrations and different types of solvents. In addition, the effects of grinding conditions on the fineness of alumina particles and the amount of generated polymer were examined. It was found that the amount of polymer could be controlled by the MMA concentration and that the rate of mechanochemical polymerization was highest in aqueous solution. The polymerization occurred in alcohol solvents, but to a limited extent because of inhibition of radical initiation.

Peroxy radicals as motional probes at the end of isolated polystyrene chains and on the cellulose surfaces in vacuum

The isolated polystyrene chains spin-labeled with peroxide radical at the free end (IPSOO) in which the chain roots were covalently bonded to the surface of microcrystalline cellulose (MCC) powder were produced by mechanochemical polymerization of styrene initiated by MCC mechanoradicals. The IPSOO was used as motional probes at the ends of isolated polystyrene chains tethered on the surface of MCC powder. Two modes for the molecular motion of IPSOO were observed. One was a tumbling motion of IPSOO on the MCC surface, defined as a train state, and another was a free rotational motion of IPSOO protruding out from the MCC surface, defined as a tail state. The temperature of tumbling motion (T tum ) of IPSOO at the train state was at 90 K with anisotropic correlation times. T tum (90 K) is extremely low compared to the glass transition temperature (T ; 373 K) of polystyrene in the bulk. At temperatures above 219 K, the IPSOO was protruded out from the MCC surface, and freely rotated at the tail state. The train–tail transition temperature (T train–tail ) was estimated to be 222 K. T tum (90 K) and T train–tail (222 K) are due to the extremely low chain segmental density of IPSOO on the MCC surface under vacuum. The interaction between IPSOO and the MCC surface is a minor contributing factor in the mobility of IPSOO on the surface under vacuum. It was found that peroxy radicals are useful probes to characterize the chain mobility reflecting their environmental conditions.

Mechanochemical polymerization – controlling a polycondensation reaction between a diamine and a dialdehyde in a ball mill

Mechanochemical polymerization displays a sustainable alternative to classical solvent-based approaches while also offering faster kinetics and an increased conversion.