Photoinitiated Radical Polymerization Research Articles

Cyclo‐bis(acyl)phosphine oxides as efficient photoinitiators for radical polymerization

Cyclo‐bis(acyl)phosphine oxides as efficient photoinitiators for radical polymerization

Bionic double-crosslinked hydrogel of poly (γ-glutamic acid)/poly (N-(2-hydroxyethyl) acrylamide) with ultrafast gelling process and ultrahigh burst pressure for emergency rescue

Injectable adhesive hydrogels combining rapid gelling with robust adhesion to wet tissues are highly required for fast hemostasis in surgical and major trauma scenarios. Inspired by the cross-linking mechanism of mussel adhesion proteins, we developed a bionic double-crosslinked (BDC) hydrogel of poly (γ-glutamic acid) (PGA)/poly (N-(2-hydroxyethyl) acrylamide) (PHEA) fabricated through a combination of photo-initiated radical polymerization and hydrogen bonding cross-linking. The BDC hydrogel exhibited an ultrafast gelling process within 1 s. Its maximum adhesion strength to wet porcine skin reached 254.5 kPa (9 times higher than that of cyanoacrylate (CA) glue) and could withstand an ultrahigh burst pressure of 626.4 mmHg (24 times higher than that of CA glue). Notably, the BDC hydrogel could stop bleeding within 10 s from a rat liver incision 10 mm long and 5 mm deep. The wound treated with the BDC hydrogel healed faster than the control groups, underlining the potential for emergency rescue and wound care scenarios.

Synthesis of Polycarboxylate Superplasticizers via Photoinitiated Radical Polymerization

Synthesis of Polycarboxylate Superplasticizers via Photoinitiated Radical Polymerization

Inducing an LCST in hydrophilic polysaccharides via engineered macromolecular hydrophobicity

Thermoresponsive polysaccharide-based materials with tunable transition temperatures regulating phase-separated microdomains offer substantial opportunities in tissue engineering and biomedical applications. To develop novel synthetic thermoresponsive polysaccharides, we employed versatile chemical routes to attach hydrophobic adducts to the backbone of hydrophilic dextran and gradually increased the hydrophobicity of the dextran chains to engineer phase separation. Conjugating methacrylate moieties to the dextran backbone yielded a continuous increase in macromolecular hydrophobicity that induced a reversible phase transition whose lower critical solution temperature can be modulated via variations in polysaccharide concentration, molecular weight, degree of methacrylation, ionic strength, surfactant, urea and Hofmeister salts. The phase separation is driven by increased hydrophobic interactions of methacrylate residues, where the addition of surfactant and urea disassociates hydrophobic interactions and eliminates phase transition. Morphological characterization of phase-separated dextran solutions via scanning electron and flow imaging microscopy revealed the formation of microdomains upon phase transition. These novel thermoresponsive dextrans exhibited promising cytocompatibility in cell culture where the phase transition exerted negligible effects on the attachment, spreading and proliferation of human dermal fibroblasts. Leveraging the conjugated methacrylate groups, we employed photo-initiated radical polymerization to generate phase-separated hydrogels with distinct microdomains. Our bottom-up approach to engineering macromolecular hydrophobicity of conventional hydrophilic, non-phase separating dextrans to induce robust phase transition and generate thermoresponsive phase-separated biomaterials will find applications in mechanobiology, tissue repair and regenerative medicine.

Grafting α-aminoketone to SMA via highly efficient amide bond and their performances as macrophotoinitiators

Water-soluble macrophotoinitiators that can realize a high photoactivity together with low migration in waterborne photopolymerization systems are very necessary. However, the precise, highly efficient preparation of macrophotoinitiators remains a substantial challenge, such as grafting side chains according to stoichiometric ratios. Herein, based on styrene maleic anhydride copolymer (SMA) prepared by photopolymerization, water soluble macrophotoinitiators SMA5k-Ns and SMA13k-Ns series with controllable structure were successfully prepared through the amino bond of α-aminoketone small-molecule photoinitiator with maleic anhydride moieties. All of them exhibited excellent water dispersion properties, and solution photopolymerizations investigation showed they can be used as photoinitiators for radical polymerization with high conversion (up to 95%) in waterborne systems under LED@365–405 nm. Furthermore, the migration stabilities of these photoinitiators in photocured hydrogels were better than those of commercial photoinitiators. High efficiency and low migration make them have great potential applications in food packaging and biological materials.

New Photocrosslinked 3D Foamed Scaffolds Based on GelMA Copolymers: Potential Application in Bone Tissue Engineering.

The production of customized polymeric hydrogels in the form of 3D scaffolds with application in bone tissue engineering is currently a topic of great interest. Based on gelatin methacryloyl (GelMa) as one of the most popular used biomaterials, GelMa with two different methacryloylation degrees (DM) was obtained, to achieve crosslinked polymer networks by photoinitiated radical polymerization. In this work, we present the obtention of new 3D foamed scaffolds based on ternary copolymers of GelMa with vinylpyrrolidone (VP) and 2-hydroxyethylmethacrylate (HEMA). All biopolymers obtained in this work were characterized by infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA), whose results confirm the presence of all copolymers in the crosslinked biomaterial. In addition, scanning electron microscopy (SEM) pictures were obtained verifying the presence of the porosity created by freeze-drying process. In addition, the variation in its swelling degree and its enzymatic degradation in vitro was analyzed as a function of the different copolymers obtained. This has allowed us to observe good control of the variation in these properties described above in a simple way by varying the composition of the different comonomers used. Finally, with these concepts in mind, biopolymers obtained were tested through assessment of several biological parameters such as cell viability and differentiation with MC3T3-E1 pre-osteoblastic cell line. Results obtained show that these biopolymers maintain good results in terms of cell viability and differentiation, along with tunable properties in terms of hydrophilic character, mechanical properties and enzymatic degradation.

Latest Advances in Highly Efficient Dye-Based Photoinitiating Systems for Radical Polymerization.

Light-activated polymerization is one of the most important and powerful strategies for fabrication of various types of advanced polymer materials. Because of many advantages, such as economy, efficiency, energy saving and being environmentally friendly, etc., photopolymerization is commonly used in different fields of science and technology. Generally, the initiation of polymerization reactions requires not only light energy but also the presence of a suitable photoinitiator (PI) in the photocurable composition. In recent years, dye-based photoinitiating systems have revolutionized and conquered the global market of innovative PIs. Since then, numerous photoinitiators for radical polymerization containing different organic dyes as light absorbers have been proposed. However, despite the large number of initiators designed, this topic is still relevant today. The interest towards dye-based photoinitiating systems continues to gain in importance, which is related to the need for new initiators capable of effectively initiating chain reactions under mild conditions. In this paper we present the most important information about photoinitiated radical polymerization. We describe the main directions for the application of this technique in various areas. Attention is mainly focused on the review of high-performance radical photoinitiators containing different sensitizers. Moreover, we present our latest achievements in the field of modern dye-based photoinitiating systems for the radical polymerization of acrylates.

Nanofibers as precursors for the rapid formation of hydrogels.

Hydrogels can be used in surgeries, which require a support material to maintain the correct anatomy. One major limitation is however the time required for the preparation of hydrogels under urgent conditions. Herein, we report a new method for a very fast preparation of hydrogels at room temperature. Nanofibers of dextran containing vinyl groups produced by electrospinning are loaded with redox- or photo-initiators for radical polymerization. Once dissolved in water, the nanofibers yield hydrogels either spontaneously or upon irradiation with UV light. We also show that the nanofibers can be loaded with active fillers so that hydrogels embedding nanocapsules are obtained. This concept could be applied for the rapid preparation of functional hydrogels which are needed as implants.

A road map on synthetic strategies and applications of biodegradable polymers.

Biodegradable polymers have emerged as fascinating materials due to their non-toxicity, environmentally benign nature and good mechanical strength. The toxic effects of non-biodegradable plastics paved way for the development of sustainable and biodegradable polymers. The engineering of biodegradable polymers employing various strategies like radical ring opening polymerization, enzymatic ring opening polymerization, anionic ring opening polymerization, photo-initiated radical polymerization, chemoenzymatic method, enzymatic polymerization, ring opening polymerization and coordinative ring opening polymerization have been discussed in this review. The application of biodegradable polymeric nanoparticles in the biomedical field and cosmetic industry is considered to be an emerging field of interest. However, this review mainly highlights the applications of selected biodegradable polymers like polylactic acid, poly(ε-caprolactone), polyethylene glycol, polyhydroxyalkanoates, poly(lactide-co-glycolide) and polytrimethyl carbonate in various fields like agriculture, biomedical, biosensing, food packaging, automobiles, wastewater treatment, textile and hygiene, cosmetics and electronic devices.

Organocatalyzed Phospha-Michael Addition: A Highly Efficient Synthesis of Customized Bis(acyl)phosphane Oxide Photoinitiators.

Addition of the P-H bond in bis(mesitoyl)phosphine, HP(COMes)2 (BAPH), to a wide variety of activated carbon-carbon double bonds as acceptors was investigated. While this phospha-Michael addition does not proceed in the absence of an additive or catalyst, excellent results were obtained with stoichiometric basic potassium or caesium salts. Simple amine bases can be employed in catalytic amounts, and tetramethylguanidine (TMG) in particular is an outstanding catalyst that allows the preparation of bis(acyl)phosphines, R-P(COMes)2 , under very mild conditions in excellent yields after only a short time. All phosphines RP(COMes)2 can subsequently be oxidized to the corresponding bis(acyl)phosphane oxides, RPO(COMes)2 , a substance class belonging to the most potent photoinitiators for radical polymerizations known to date. Thus, a simple and highly atom economic method has been found that allows the preparation of a broad range of photoinitiators adapted to their specific field of application even on a large scale.

Experimental study on mechanism of stable drag reduction with hydrogel interface

The hydrogel is a novel material with drag-reducing ability, which has great potential to be applied in marine applications. In this paper, a series of superhydrophilic hydrogels were prepared by photoinitiated radical polymerization. The Couette flow and particle image velocimeter (PIV) observation in the water tunnel were conducted to investigate the drag-reducing characteristics of the prepared hydrogels. The results show that the hydrogel thickness of 1500 µm is the critical value corresponding to the maximum drag reduction rate of about 68%. The drag reduction is induced by the boundary slip phenomenon on the hydrophilic surface, and the further mechanism can be explained in two aspects. On one hand, the generated vorticities in the grooves between the macroscopic convex structures of the hydrogel induce the fluid sliding state converted into the rolling state. This state transformation reduces the near-wall velocity gradient, and thus promotes the generation of boundary slip. On the other hand, fluorescence particle experiments reveal that there exists water exchange between the inside and outside of the hydrogel. This exchange would promote the relative velocity, and thus strengthens the boundary slip. The present work is expected to make a certain contribution to reveal the drag reduction mechanism of hydrogel.

Large-molecular-weight acyldiphenylphosphine oxides as low-mobility type I photoinitiator for radical polymerization

In recent years, the light source for photopolymerization technology is evolving from energy-hungry mercury lamps to the safer light-emitting diodes (LEDs), and it is urgent to develop new photoinitiator adapted to the photopolymerization system with LED light source. Some acyldiphenylphosphine oxide photoinitiators have been designed and developed for LED light source, but their application is severely limited in the fields of food packing, medical equipment, environmentally-friendly product etc. due to their high mobility in photocured polymers. In this study, eight acyldiphenylphosphine oxide molecules (DAPO-1 ∼ DAPO-8) were synthesized by introducing large molecular weight groups and their UV–visible absorption, photodegradation quantum yield, photopolymerization properties, mobility and solubility in monomer were determined. Thereinto, photoinitiators show lower mobility than TPO, the photoinitiator commonly used in industry, as well as good solubility in monomers and excellent photopolymerization performance. Therefore, they can serve as potential substitutes for commercial TPO, especially in the application of low-migration photocurable system.

Superior, Environmentally Tolerant, Flexible, and Adhesive Poly(ionic liquid) Gel as a Multifaceted Underwater Sensor.

In recent years, gel-based sensors have been widely considered and fully developed. However, it is of vital importance, yet rather challenging to achieve a multifaceted gel, which can unify the advantages of favorable conductivity, high adhesion, excellent environmental resistance, and so forth and be applied in various harsh conditions. Herein, an ideal, extremely stable, adhesive, conductive poly(ionic liquid) gel (PILG) was designed via a one-step photoinitiated radical polymerization based on 1-vinyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide (VBIm-NTf2) cross-linked with ethylene glycol dimethacrylate (EGDMA) in methyltributylammonium bis(trifluoromethanesulfonyl)imide (N1444-NTf2) medium. There are abundant hydrophobic butyl chains and fluorinated groups in VBIm-NTf2 and N1444-NTf2, which can impart the PILG with stable conductivity, excellent environmental tolerance, and adhesion even in water due to the ion-dipole and ion-ion interactions. The resulting PILG can be assembled as a soft and smart sensor that can be applied in specific conditions such as underwater or undersea and even in dynamic water, achieving a stable signal transmission. Meanwhile, the PILG can be utilized as a flexible electrode to convey ECG signals in air or water whether it is in the static or dynamic state. Therefore, it is envisioned that this novel PILG will serve as a hopeful electrical device for signal detection and healthy management in specific environments.

Liquid Metal Nanoparticles as a Highly Efficient Photoinitiator to Develop Multifunctional Hydrogel Composites

Liquid metal (LM) composites are a class of emerging soft multifunctional materials that are promising for a variety of applications, yet the chemistry properties of LM have not been fully understood. Here, we report that LM nanoparticles can directly perform as a photoinitiator for radical polymerization and the in situ development of highly tough and multifunctional LM hydrogel composites. It is revealed that the photocatalytic activity of LM nanoparticles originates from the oxide layer on LM. Significantly, positively charged metal-organic framework (MOF) nanoparticles are used to stabilize LM nanoparticles in aqueous solutions, where the MOF can anchor on the surface of LM nanoparticles by electrostatic interaction while helping to preserve the unshielded oxide layer, therefore realizing the highly efficient photoinitiation and polymerization. The LM nanoparticle-initiated photopolymerization is shown to develop hydrogel composites featuring excellent stretchability, stimuli responsiveness, and sustained photocatalytic activity. The photocatalytic polymerization initiated by LM nanoparticles not only deepens the understanding on the semiconductor properties of the oxide skin on LM but also broadens the application scenarios of multifunctional LM/polymer composites in smart materials, wearable electronics, and soft robotics.

New acyl phosphine oxides as high-performance and low migration type I photoinitiators of radical polymerization

Two low migration acylphosphine oxide photoinitiators (APO and DAPO) containing unsaturated CC double bonds have been designed and synthesized for free radical polymerization. The properties and performances of APO and DAPO in the free radical polymerization of trimethylolpropane triacrylate (TMPTA) were evaluated and compared with the commercial photoinitiator 2,4,6-trimethyl(phenyl) diphenyl oxide (TPO). The results show that DAPO exhibited the best double bond conversion (DC) of TMPTA in the photoinitiators tested under the same reaction conditions. The migration ratio of APO and DAPO was 2/3 and 1/3 of that of TPO respectively indicating lower migration than the conventional photoinitiator, and the solubility of DAPO in monomers was close to that of TPO, which provided the possibility for the industrial application of DAPO.

High-Performance UV-Vis Light Induces Radical Photopolymerization Using Novel 2-Aminobenzothiazole-Based Photosensitizers.

The popularity of using the photopolymerization reactions in various areas of science and technique is constantly gaining importance. Light-induced photopolymerization is the basic process for the production of various polymeric materials. The key role in the polymerization reaction is the photoinitiator. The huge demand for radical and cationic initiators results from the dynamic development of the medical sector, and the optoelectronic, paints, coatings, varnishes and adhesives industries. For this reason, we dealt with the subject of designing new, highly-efficient radical photoinitiators. This paper describes novel photoinitiating systems operating in UV-Vis light for radical polymerization of acrylates. The proposed photoinitiators are composed of squaraine (SQ) as a light absorber and various diphenyliodonium (Iod) salts as co-initiators. The kinetic parameters of radical polymerization of trimethylolpropane triacrylate (TMPTA), such as the degree of double bonds conversion (C%), the rate of photopolymerization (Rp), as well as the photoinitiation index (Ip) were calculated. It was found that 2-aminobenzothiazole derivatives in the presence of iodonium salts effectively initiated the polymerization of TMPTA. The rates of polymerization were at about 2 × 10−2 s−1 and the degree of conversion of acrylate groups from 10% to 36% were observed. The values of the photoinitiating indexes for the most optimal initiator concentration, i.e., 5 × 10−3 M were in the range from 1 × 10−3 s−2 even to above 9 × 10−3 s−2. The photoinitiating efficiency of new radical initiators depends on the concentration and chemical structure of used photoinitiator. The role of squaraine-based photoinitiating systems as effective dyeing photoinitiators for radical polymerization is highlighted in this article.

Carbon nitride‐coated transparent glass vials as photoinitiators for radical polymerization

AbstractBenign polymerization routes offer new perspectives in current polymer technology. Especially for automated or continuous flow synthesis of polymers, new devices and principles have to be considered by the means of minimizing addition or separation sequences as well as the type of a polymer initiation. Near‐UV and visible light‐induced polymerization utilizing metal‐free semiconductor polymeric carbon nitride (pCN) as heterogeneous photocatalyst was a first step into this direction. Moving from heterogeneous powder catalysis (which still requests catalyst separation) to surface photocatalysis via coating glass tubes or vials with pCN thin films is presented. Performance and effectivity of those photoactive reactors are proven by free radical photopolymerization of variety of monomers. Reusability of vials is demonstrated via reversible addition‐fragmentation chain‐transfer polymerization‐assisted block copolymer synthesis. This strategy eliminates the necessity of adding or removing initiators, works at room temperature, and offers a platform for cheap and effective polymer synthesis at the age of automated synthesis.

SILICON-CONTAINING OLIGOMERIC AZOINITIATORS IN THE SYNTHESIS OF BLOCK COPOLYMERS

The aim of the work was to develop methods for the synthesis and study of the properties of silicon-containing oligomeric azo- and polyazoinitiators based on bis-γ-hydroxypropylpolysiloxane (HPS) and bis-γ-aminopropylpolysiloxane (APS). Silicon-containing oligomeric azoinitiators using HPS were synthesized on the basis of cyclohexanone azo-bis-isobutyrohydrazone (AGN-CH) and bis-γ-hydroxypropylpolysiloxane bifunctional macrodiisocyanate (MDIHPS). MDIHPS was obtained by the interaction of GPS with 2,4 toluene diisocyanate (2,4-TDI). Oligomeric azoinitiators have been obtained, which have the structure RXR and (RX)nR, where R is a propylpolysiloxane block, X is a azo initiator block. For the synthesis of an oligomeric azo initiator based on bis-γ-aminopropyl polysiloxane (APS), a method was first developed for the synthesis of a monomeric azo initiator with terminal oxadiazolinylcarbamanate isocyanate groups (AGN-NCO) by the interaction of AGN-CH and 2,4-TDI at a molar ratio of 1: 2. On the basis of the obtained AGN-NCO and APS at a molar ratio of AGN-NCO: APS = 1: 1, an oligomeric azo initiator (OAI APS-P) was synthesized, which has the structure (RX)nR, where R is a propylpolysiloxane block, X is an azo initiator block. The structures of monomeric and oligomeric azo initiators have been studied by UV and IR spectroscopy, and the kinetic regularities of their synthesis have been calculated. On the basis of oligomeric azo initiators and styrene, block copolymers of the (AB)nA type were obtained by the method of thermal and photoinitiated radical polymerization, where A is a propylpolysiloxane block, B is an oligosyrene block with a constant value of the organosilicon block and a different size of the oligostyrene block. The structure of block copolymers was investigated by IR spectroscopy. It was shown that during photopolymerization, oligostyrene blocks of shorter length are formed than during thermopolymerization, and possible oxidation processes. The study of relaxation transitions by DSC in oligostyrene and propylpolysiloxane blocks of the BCP showed that the common heat capacity curves are the presence of two jumps in the heat capacity at the glass transition temperatures of the polysiloxane and oligostyrene microphase. A slight shift in the glass transition temperature of polysiloxane microphases in BCP towards higher temperatures compared to the homopolymer may be associated with the effect of oligostyrene microphase. With a decrease in the length of the oligosyrene block, a low-temperature shift in the glass transition temperature of oligostyrene blocks relative to the homopolymer and a depression of ∆Cp,2 are observed, which is associated with the suppression of mobility in oligodienic microphases by less mobile propylpolysiloxane blocks.

Light-Mediated Polymerization Switch

Key words photoinitiated radical polymerization - coordination insertion - polymerization switch

Morphology effect on zinc oxide quantum photoinitiators for radical polymerization.

Semiconductor nanocrystal based photoinitiators, quantum PIs, are a viable alternative to organic photoinitiators demonstrating unique advantages, including a broad and tunable excitation window, limited migration, and more. Aiming towards efficient quantum PIs with tunable properties, a deeper understanding of the relationships between the nanoparticle properties and their efficiency is required. Herein, we studied the morphological effect on ZnO nanocrystals functioning as photoinitiators in both water-based and solvent-free formulations by comparing rod and pyramidal shaped particles of similar volumes and nearly identical surface area. Superior polymerization performances are measured for the nanorods. Photocatalytic characterization including oxygen consumption and reactive oxygen species formation as well as dyes reduction and oxidation, also showed enhanced activities for the nanorods. The different performances were attributed to the anisotropic nanorod morphology which is beneficial for charge separation as well as to the presence of a reactive [0001] facet in the nanorods, which is known to increase the adsorption of molecular oxygen and anionic molecules, thus affecting the catalytic activity. These observations, along with the higher photoinitiation efficiency of the ZnO nanorods, bring them closer to functionality as photoinitiators in numerous photopolymerization applications.