Polymerizable Groups Research Articles

Reconfigurable Visible Light-Driven Liquid Crystalline Network Showing Off-Equilibrium Motions Enabled by Mesogen-Grafted Donor-Acceptor Stenhouse Adducts.

Liquid crystalline network (LCN)-based soft actuators have opened up great opportunities to fabricate emerging and intriguing smart materials, serving as potential building blocks for intelligent soft robotics. Endowing LCN actuators with complex responsive behaviors to enhance their intelligence is both challenging and highly demanded. Herein, Donor-Acceptor Stenhouse Adducts (DASAs) molecules with rod-like mesogen and the polymerizable group are judiciously designed and synthesized, which is strong-colored at linear form and de-coloration at cyclic form after visible light. In the colored state, the DASA presents a striking photothermal effect that is capable of driving the motions of LCN film. Upon visible light irradiation, the DASA becomes colorless, making the diminishing photothermal effect. The light-gated switching of the photothermal effect renders the LCN films to be reconfigurable and perform off-equilibrium motions. The varying glass transition temperature of LCN matrix endowing tunable isomerization rates of DASAs and the equilibrium balance of photo- and thermal-isomerization at different temperatures in LCN-P-DASA film mainly guiding the off-equilibrium or stable motions, providing high adjustability of the novel visible light-driven LCN actuators. The multiply modulated LCN-P-DASA film holds great potential in constructing complex visible light-driven soft actuators based on the synergetic effect and interactions of photochemical and photothermal effects.

Helical Star-Shaped Bottlebrush Polymers: From Controlled Synthesis to Tunable Photoluminescence and Circularly Polarized Luminescence.

The controlled synthesis of star-shaped bottlebrush polymers with tunable topologies is a challenge. However, such materials may exhibit distinct photoluminescence properties. Bottlebrush polymers have polymerization-induced emission (PIE) properties due to their aggregated side chains, and aggregation-induced emission (AIE) is also a unique luminescent property. In this work, we prepared a variety of highly active alkyne Pd catalysts and polymerized poly(L/D-lactic acid) macromonomers containing polymerizable phenylisocyanide groups as end groups to obtain a variety of topologically structured bottlebrush polymers with controllable molecular weights and narrow molecular weight distributions. Bottlebrush polymers with tetraphenyl ethylene (TPE) units as the core exhibit tunable photoluminescence and circularly polarized luminescence properties. We propose that such properties are due to the unique AIE characteristics of the TPE unit combined with the PIE characteristics of the bottlebrush polymer.

Differences Photopolymerizations and Characterizations of Monomers Liquid Crystal between Mesogen Reactive RM 257 and Cholesteryl Acrylate using method of UV Curing

Abstract Mesogen reactive RM257 and cholesteryl acrylate are two types of liquid crystal with the characteristic property of possesing polymerizable groups. Cholesteryl acrylate has interesting properties that can form a helical spiral structure. Previous research in maintaining the helical structure has not been maximized. In this study, we will explain how the UV curing process is a way to fix the helical structure. Monomer phase of cholesteryl acrylate only appears at mesophase temperature, in order to maintain the helical structure of the cholesterl acrylic compound is polymerized. Mesogen reactive RM257 is monomer liquid crystal that acrylate functions as back bone polymer chain. Cholesteryl acrylate and RM257 each monomers is polymerized using UV light with 55 watt of wavelength which has 365 nm. The polymerization process produces a new functional group formed by C-O esters at wave numbers 1047 cm−1 and 1055 cm−1. XRD diffraction pattern showed peaks at 2θ in 7.5°,15°, and 20°. Photo SEM image showed crosslinked morphology structure. Based on the results of this study, it is hoped that the polymer RM257 and acrylate coliform can be smart materials for sensor applications and further technological material composites.

Bioderived Thiol-Ene Emulsion Polymerization for Hybrid Latex Particles.

The thiol-ene emulsion polymerization of three dienes synthesized from bioderived compounds, and subsequent preparation of core-shell polymer latexes, is reported. Levoglucosan (LGA), levogucosenone (LGO) and isosorbide were first modified with 4-pentenoic acid to install polymerizable groups. These monomers were used along with a dithiol to prepare poly(thioether) particles via ab initio emulsion polymerization using potassium persulfate as initiator and sodium dodecyl sulfate as surfactant. The structure of the diene significantly influenced the size of the resulting polymer latex particles. Given their low glass transition temperature, the LGA-derived poly(thioether) particles were used as a seed for the seeded emulsion polymerization of either styrene or methyl methacrylate. Core-shell latex particles with a high Tg core and a low Tg bioderived shell were formed, as verified by electron microscopy and in agreement with theoretical predictions of the equilibrium particle morphology based on the interfacial tensions of each particle phase.

Photopolymerization Approach to Advanced Polymer Composites: Integration of Surface-Modified Nanofillers for Enhanced Properties.

The incorporation of functionalized nanofillers into polymers via photopolymerization approach has gained significant attention in recent years due to the unique properties of the resulting composite materials. Surface modification of nanofillers plays a crucial role in their compatibility and polymerization behavior within the polymer matrix during photopolymerization. This review focuses on the recent developments in surface modification of various nanofillers, enabling their integration into polymer systems through photopolymerization. The review discusses the key aspects of surface modification of nanofillers, including the selection of suitable surface modifiers, such as photoinitiators and polymerizable groups, as well as the optimization of modification conditions to achieve desired surface properties. The influence of surface modification on the interfacial interactions between nanofillers and the polymer matrix is also explored, as it directly impacts the final properties of the nanocomposites. Furthermore, the review highlights the applications of nanocomposites prepared by photopolymerization, such as sensors, gas separation membranes, purification systems, optical devices, and biomedical materials. By providing a comprehensive overview of the surface modification strategies and their impact on the photopolymerization process and the resulting nanocomposite properties, this review aims to inspire new research directions and innovative ideas in the development of high-performance polymer nanocomposites for diverse applications.

Octahedral molybdenum cluster complex with glycolate ligands and study of its activity in polyurethane polymerization process

Octahedral metal clusters [{M6X8}L6]2– (where M = Mo2+ or W2+, X = Cl–, Br– or I–, and L is an apical ligand typically with a charge of 1–) have shown promise in a great variety of applications, ranging from solar energy and catalysis to cancer diagnostics and therapy. However, these clusters are not stable in water – the most widely used medium in many practical fields. An effective way to utilize and stabilize these compounds is to incorporate them into organic matrices. Along with direct impregnation, clusters can be used as monomers in polymerization process due to the ease of an addition of polymerizable functional groups in cationic part or in apical ligand environment. In this work, new cluster with six terminal glycolate ligands, (Bu4N)2[{Mo6I8}(OOCCH2OH)6], has been obtained and studied using FTIR, TGA, EDX, etc. Cluster luminescence has been studied in the temperature range of 77–300 K. As have been demonstrated experimentally and theoretically, by the DFT calculations, the coordination of glycolic acid to the cluster drastically reduces the activity of the –OH group in the polymerization of polyurethane.

A low mobility UV-LED benzophenone photoinitiator

With the increase frequency of food safety incidents caused by migrating photoinitiators over the past few years, as well as people’s growing awareness of safety and environmental protection, the development of low-migration UV-LED photoinitiators has become increasingly crucial. A photoinitiator 3-vinyl-4-dimethylaminobenzophenone (NVBP) with both hydrogen donor and polymerizable double bond group was prepared and characterized by 1H NMR and 13C NMR. A systematic study of the photopolymerization kinetics of NVBP was explored by the Real-Time Fourier Transform Infrared Spectrometer. The results showed a good initiation efficiency of acrylate monomers under 365 nm/405 nm light source with double bond conversion up to 94.6 % and 79.7 %. In addition, NVBP has low mobility, which is important to facilitate photoinitiator applications. This work proves that NVBP is an excellent UV-LED photoinitiator.

Effect of Gold Nanoparticle Size on Regulated Catalytic Activity of Temperature-Responsive Polymer-Gold Nanoparticle Hybrid Microgels.

Gold nanoparticles (AuNPs) possess attractive electronic, optical, and catalytic properties, enabling many potential applications. Poly(N-isopropyl acrylamide) (PNIPAAm) is a temperature-responsive polymer that changes its hydrophilicity upon a slight temperature change, and combining PNIPAAm with AuNPs allows us to modulate the properties of AuNPs by temperature. In a previous study, we proposed a simpler method for designing PNIPAAm-AuNP hybrid microgels, which used an AuNP monomer with polymerizable groups. The size of AuNPs is the most important factor influencing their catalytic performance, and numerous studies have emphasized the importance of controlling the size of AuNPs by adjusting their stabilizer concentration. This paper focuses on the effect of AuNP size on the catalytic activity of PNIPAAm-AuNP hybrid microgels prepared via the copolymerization of N-isopropyl acrylamide and AuNP monomers with different AuNP sizes. To quantitatively evaluate the catalytic activity of the hybrid microgels, we monitored the reduction of 4-nitrophenol to 4-aminophenol using the hybrid microgels with various AuNP sizes. While the hybrid microgels with an AuNP size of 13.0 nm exhibited the highest reaction rate and the apparent reaction rate constant (kapp) of 24.2 × 10-3 s-1, those of 35.9 nm exhibited a small kapp of 1.3 × 10-3 s-1. Thus, the catalytic activity of the PNIPAAm-AuNP hybrid microgel was strongly influenced by the AuNP size. The hybrid microgels with various AuNP sizes enabled the reversibly temperature-responsive on-off regulation of the reduction reaction.

Preparation and photocuring performance of itaconic acid-derived hyperbranched macromers with internal and terminal C[dbnd]C bonds catalyzed by tetramethylguanidine

A series of hyperbranched polymers derived from biomass itaconic acid was prepared via aliphatic nucleophilic substitution polycondensation reaction under mild conditions by using bis(2-bromoethyl) itaconate and trimeric acid as A2 and B3 monomers, respectively, and tetramethylguanidine as catalyst. On this basis, the hyperbranched macromers that contained C = C double bonds in the internal skeleton and the periphery were obtained by further adding A1 monomer (2-bromoethyl acrylate) directly into the reaction system. The successful synthesis of these macromers were confirmed via proton nuclear magnetic resonance, Fourier transform infrared and gel permeation chromatography. The results of photo-differential scanning calorimetry and rheological experiments showed that these macromers exerted a positive effect on the ultraviolet (UV) curing of commercial resin. The properties of cured splines and coatings, such as mechanical properties, pencil hardness, and thermal stability, were considerably improved with the addition of hyperbranched macromers. They were significantly better than those of linear macromers and macromers that contained polymerizable groups only in the inner framework or their terminal units. The results show that both the inner and terminal C = C double bonds of hyperbranched macromers can participate in UV cross-linking. Thus, such macromers may be used as potential additives for high-performance UV curable coatings.

Highly Ordered Gyroid Nanostructured Polymers: Facile Fabrication by Polymerizable Pluronic Surfactants.

Highly ordered, network-nanostructured polymers offer compelling geometric features and application potential. However, their practical utilization is hampered by the restricted accessibility. Here, we address this challenge using commercial Pluronic surfactants with a straightforward modification of tethering polymerizable groups. By leveraging lyotropic self-assembly, we achieve facile production of double-gyroid mesophases, which are subsequently solidified via photoinduced cross-linking. The exceptionally ordered periodicities of Ia3d symmetry in the photocured polymers are unambiguously confirmed by synchrotron small-angle X-ray scattering (SAXS), which can capture single-crystal-like diffraction patterns. Electron density maps reconstructed from SAXS data complemented by transmission electron microscopy analysis further elucidate the real-space gyroid assemblies. Intriguingly, by tuning the cross-linking through thiol-acrylate chemistry, the mechanical properties of the polymer are modulated without compromising the integrity of Ia3d assemblies. The 3-D percolating gyroid nanochannels demonstrate an ionic conductivity that surpasses that of disordered structures, offering promising prospects for scalable fabrication.

Cryogels Based on Poly(2-oxazoline)s through Development of Bi- and Trifunctional Cross-Linkers Incorporating End Groups with Adjustable Stability.

1,4-Bis(iodomethyl)benzene and 1,3,5-tris(iodomethyl)benzene were used as initiators for the cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline (EtOx) and its copolymerization with tert-butyl (3-(4,5-dihydrooxazol-2-yl)propyl)carbamate (BocOx) or methyl 3-(4,5-dihydrooxazol-2-yl)propanoate (MestOx). Kinetic studies confirmed the applicability of these initiators. Termination with suitable nucleophiles resulted in two- and three-armed cross-linkers featuring acrylate, methacrylate, piperazine-acrylamide, and piperazine-methacrylamide as polymerizable ω-end groups. Matrix-assisted laser desorption/ionization mass spectrometry and nuclear magnetic resonance (NMR) spectroscopy confirmed the successful attachment of the respective ω-end groups at all initiation sites for every prepared cross-linkers. Except for acrylate, each ω-end group remained stable during deprotection of BocOx containing cross-linkers. The cryogels were prepared using EtOx-based cross-linkers, as confirmed by solid-state NMR spectroscopy, scanning electron microscopy, and thermogravimetric analysis. Stability tests revealed a complete dissolution of the acrylate-containing gels at pH = 14, whereas the piperazine-acrylamide-based cryogels featured excellent hydrolytic stability.

Orthogonal Postsynthetic Copolymerization of Hydrogen‐Bonded Organic Frameworks into a PolyHOF Membrane

AbstractHydrogen‐bonded organic frameworks (HOFs) have shown promise in various fields; however, the construction of HOF/polymer hybrid membranes that can maintain both structural and functional integrity remains challenging. In this study, we here fabricated a new HOF (HOF‐50) with reserved polymerizable allyl group via charge‐assisted H‐bonds between the carboxylate anion and amidinium, and subsequently copolymerized the HOF with monomers to construct a covalently bonded HOF/polymer hybrid (polyHOF) membrane. The resulting polyHOF membrane not only exhibits customizable mechanical properties and extreme stability, but also shows an exceptional ratiometric luminescent temperature‐sensing function with very high sensitivity and visibility even when the lanthanide content is two orders of magnitude lower than that of the reported mixed‐lanthanide metal–organic frameworks (MOFs) and lanthanide‐doped covalent organic frameworks (COFs). This orthogonal postsynthesis copolymerization strategy may provide a general approach for preparing covalently connected HOF/polymer hybrid membranes for diverse applications.

Orthogonal Postsynthetic Copolymerization of Hydrogen-Bonded Organic Frameworks into a PolyHOF Membrane.

Hydrogen-bonded organic frameworks (HOFs) have shown promise in various fields; however, the construction of HOF/polymer hybrid membranes that can maintain both structural and functional integrity remains challenging. In this study, we here fabricated a new HOF (HOF-50) with reserved polymerizable allyl group via charge-assisted H-bonds between the carboxylate anion and amidinium, and subsequently copolymerized the HOF with monomers to construct a covalently bonded HOF/polymer hybrid (polyHOF) membrane. The resulting polyHOF membrane not only exhibits customizable mechanical properties and extreme stability, but also shows an exceptional ratiometric luminescent temperature-sensing function with very high sensitivity and visibility even when the lanthanide content is two orders of magnitude lower than that of the reported mixed-lanthanide metal-organic frameworks (MOFs) and lanthanide-doped covalent organic frameworks (COFs). This orthogonal postsynthesis copolymerization strategy may provide a general approach for preparing covalently connected HOF/polymer hybrid membranes for diverse applications.

Polymeric carbon nitrides/3D honeycomb poly(ionic liquid)s photoreactor with improved photo-electric property for efficient wastewater treatment

Here we report a strategy to synthesize efficient polymeric carbon nitrides/3D honeycomb poly(ionic liquid)s photoreactor. The initial parent polymeric carbon nitrides (PCN) were synthesized by sintering precursor formed by self-assembling molecules of cyanuric acid and melamine. Ionic liquids with polymerizable groups polymerized in situ with crosslinkers in a system dispersed in PCN to synthesize a photoreactor. Impressively, the obtained photoreactors have structurally stable nanoparticle morphology in a dry state and a transparent 3D network structure in a swelling state. Their successful formation, swelling ability and morphology were fully characterized by XRD, WAXS, FT-IR, SEM, XPS, TEM and N2 adsorption/desorption isotherm. UV–vis DRS, PL spectra, and photocurrent tests showed the improved photo-electric property of the photoreactor, which was attributed to the 3D network honeycomb structure improving the contact between the active centres in the reactor and the reaction substrate and the improving electron-hole separation efficiency of PCN by excellent electron transfer ability of poly(ionic liquid)s. These synthesized photoreactors could highly efficiently degrade the anionic dyes, such as methyl orange and acid blue 93, under a metal halide lamp or even natural sunlight.

Controllable Catalytic Activity of Temperature-Responsive Polymer Hybrid Microgels Designed Using a Gold Nanoparticle Monomer with Polymerizable Groups

Controllable Catalytic Activity of Temperature-Responsive Polymer Hybrid Microgels Designed Using a Gold Nanoparticle Monomer with Polymerizable Groups

Carbamate-Protected (BOC and O-NB) 2-Aminopyrimidinedione-Based Janus G-C Nucleobase Motifs as Building Blocks for Supramolecular Assembly and Smart Polymers.

In this paper, we report "carbamate protected" 2-aminopyrimidinedione-based Janus G-C nucleobases (2-APD Janus G-C nucleobases) featuring polymerizable groups and self-complementary triple H-bonding motifs DDA and AAD as building blocks for developing smart polymers and self-healing materials. The carbamate-masked H-bonding motif, cleavable under acidic (BOC group) or photocleavable (O-nitrobenzyl group) conditions, would facilitate the synthesis of smart polymers by alleviating aggregation during polymerization which in turn would exclude self-assembly-assisted solubility issues. Ready accessibility in excellent yields coupled with the possibility for facile introduction of polymerizable groups would make these building blocks excellent candidates for diverse polymerization applications.

Synthesis of polymerizable quaternary ammonium bromides and their efficacy against pathogenic and food spoilage bacteria

Despite rigorous cleaning and sanitization protocols, food manufacturing facilities can harbor persistent microorganisms that can cause post processing contamination leading to food safety and food spoilage issues. Of particular concern are ‘growth niches’, regions within a manufacturing facility more likely to accumulate water and debris because they are outside the zones of routine cleaning and sanitization. Such growth niches present a challenge in controlling post-processing microbial contamination which can affect the safety and shelf life of foods and beverages. In recent years, researchers have explored using antimicrobial and nonfouling coatings to control microbial persistence and cross contamination. A challenge in identifying effective coatings is the limited research on efficacy of antimicrobial monomers (suitable for polymerization into antimicrobial coatings) on microorganisms relevant in food safety and spoilage. In this work, we synthesize and characterize the efficacy of five antimicrobial quaternary ammonium bromide (QAB) monomers against pathogenic and food spoilage organisms. The QAB monomers are end-capped with dihydroxy moieties suitable for subsequent polymerization into antimicrobial polyurethanes and polyesters. N,N-bis(2-hydroxyethyl)-N-methyl-N-R-1-ammonium bromides (R= -octan {C8QAB}, -decan {C10QAB}, -dodecan {C12QAB}, -hexadecan {C16QAB}, -octadecan {C18QAB}) were synthesized and characterized using spectral techniques (Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy). Minimum inhibitory concentrations were determined against relevant food safety and food spoilage bacteria Listeria monocytogenes, Salmonella Typhimurium, Escherichia coli, and Pseudomonas poae. Sixteen and eighteen carbon length QAB monomers inhibited growth of L. monocytogenes and P. poae at a concentration of 3 ppm, while sixteen carbon length QAB monomerinhibited growth of Salmonella Typhimurium at 26 ppm and against Escherichia coli at 13 ppm. Quaternary ammonium compounds capped with polymerizable end groups such as those reported here offer an opportunity to reduce persistence and cross-contamination of food pathogens and food spoilage bacteria with particular relevance in growth niches outside of routine cleaning and sanitization regimens.

Polymerizable Solvent-free Organic Liquids: A New Approach for Large Area Flexible and Foldable Luminescent Films.

The high demand for light-emitting and display devices made luminescent organic materials as attractive candidates. Solvent-free organic liquids are one of the promising emitters among them due to the salient features. However, the inherent limitations of forming sticky and noncurable surfaces must be addressed to become an alternate emitter for large-area device applications. Herein, we functionalized solvent-free organic liquids having monomeric emission in bulk with polymerizable groups to improve the processability. The polymerizable group on carbazole, naphthalene monoimide, and diketopyrrolopyrrole-based solvent-free liquid emitters enabled on-surface polymerization. These emitters alone and in combinations can be directly coated on a glass substrate without the help of solvents. Subsequent photo or thermal polymerization leads to stable, non-sticky, flexible, foldable, and free-standing large-area films with reasonably high quantum yield. Our demonstration of the tunable and white light-emitting films using polymerizable solvent-free liquids might be a potential candidate in flexible/foldable/stretchable electronics. The new concept of polymerizable liquid can be extended to other functional features suitable for futuristic applications.

Polymerizable Solvent‐free Organic Liquids: A New Approach for Large Area Flexible and Foldable Luminescent Films

AbstractThe high demand for light‐emitting and display devices made luminescent organic materials as attractive candidates. Solvent‐free organic liquids are one of the promising emitters among them due to the salient features. However, the inherent limitations of forming sticky and noncurable surfaces must be addressed to become an alternate emitter for large‐area device applications. Herein, we functionalized solvent‐free organic liquids having monomeric emission in bulk with polymerizable groups to improve the processability. The polymerizable group on carbazole, naphthalene monoimide, and diketopyrrolopyrrole‐based solvent‐free liquid emitters enabled on‐surface polymerization. These emitters alone and in combinations can be directly coated on a glass substrate without the help of solvents. Subsequent photo or thermal polymerization leads to stable, non‐sticky, flexible, foldable, and free‐standing large‐area films with reasonably high quantum yield. Our demonstration of the tunable and white light‐emitting films using polymerizable solvent‐free liquids might be a potential candidate in flexible/foldable/stretchable electronics. The new concept of polymerizable liquid can be extended to other functional features suitable for futuristic applications.

Novel Zinc(II) Phthalocyanine Dyes for Color Photoresists

AbstractColor photoresists are the key materials for the fabrication of color filters (CFs). Organic dyes offer a promising alternative to the conventional pigment-based system to make CFs with higher resolution. However, the stability of dye molecules is an urgent problem to be solved. Herein, we designed and synthesized a series of highly stable zinc phthalocyanine dyes containing polymerizable acrylamide groups. Upon light exposure, dense and insoluble network structures were formed in the prepared CFs, which increase the thermal stability and anti-migration capacity of these dyes.