Fragmentation Chain Transfer Agent Research Articles

Noncorrosive Pressure-Sensitive Adhesives of Acryl Polymers by Sulfur-Free Addition–Fragmentation Chain Transfer Agents

Noncorrosive Pressure-Sensitive Adhesives of Acryl Polymers by Sulfur-Free Addition–Fragmentation Chain Transfer Agents

Polymerizable alkyl 2-(tosylmethyl)acrylates: Highly efficient addition-fragmentation chain transfer agents for the development of low shrinkage dental composites

One of the major drawbacks for restorative dentistry is the polymerization shrinkage and the consequential shrinkage stress in methacrylate-based dental composites. An efficient way to reduce shrinkage stress is the incorporation of addition fragmentation chain transfer agents (AFCT agents). In this contribution, five novel polymerizable allyl sulfones were synthesized in four to five steps. A photo-DSC study was carried out in order to evaluate the influence of the addition of each AFCT agent on the polymerization rate of a dimethacrylate-based monomer mixture. The glass transition temperature (Tg) of the resulting networks was measured using DMTA. Dental composites based on these new chain transfer agents (CTAs) were prepared. A combination of camphorquinone, ethyl 4-(dimethylamino)benzoate and bis-(4-t-butylphenyl)-iodonium hexafluorophosphate was selected as photoinitiator system. Low shrinkage force values, suitable ambient light working time and excellent mechanical properties were obtained for all CTA based materials. Composites based on three of the synthesized CTAs even exhibited higher flexural modulus than the corresponding CTA-free material. Furthermore, a significant reduction of unreacted CTA leaching was found if a polymerizable moiety was introduced in the CTA structure. Hence, the incorporation of polymerizable allyl sulfones in dental composites is a promising strategy to obtain low shrinkage materials exhibiting improved biocompatibility.

Controlled Polymerization of N‐Vinyl Imidazole, N‐Vinyl Pyrrolidone, and N‐Vinyl Carbazole with Dithiocarbamates toward High Molar Mass Polymers

AbstractAchieving control over the polymerization of less activated monomers like N‐vinyl carbazole (NVC), N‐vinyl pyrrolidone (NVP), and N‐vinyl imidazole (NVIm) to produce high molar mass polymers poses a significant challenge. To accomplish this, eight different dithiocarbamate‐based reversible addition–fragmentation chain transfer (RAFT) agents are synthesized and employed to polymerize NVIm, NVC, and NVP in order to understand and establish a suitable agent for their controlled polymerization to achieve high molar mass polymers. Chain end presence of these RAFT‐derived polymers is established through 1H NMR studies. Further, these active chain ends are used for chain extension reactions to prepare block copolymers. Synthesized RAFT agents 04, 05, 06, and 08 that are bearing primary leaving groups (methyl 2‐acetate, ethyl 2‐acetate, tert‐butyl 2‐acetate, and cyanomethane) display moderate to good control over the polymerization of NVIm and NVC. Among these, RAFT agent‐08 with cyanomethane leaving group produces poly(NVIm) and poly(NVC) with the highest molar masses of 44 670 Da (1.52) and 53 620 Da (1.4), respectively. Interestingly, RAFT agents bearing both secondary and primary leaving groups show good control over the NVP polymerization. Notably, RAFT agent‐02 with ethyl‐2‐propionate leaving group yields poly(NVP) with the highest molar mass of 89 450 Da and dispersity of 1.43.

A Strategy for Controlling the Polymerizations of Thiyl Radical Propagation by RAFT Agents

AbstractThe ability to extend the polymerizations of thiyl radical propagation to be regulated by existing controlled methods would be highly desirable, yet remained very challenging to achieve because the thiyl radicals still cannot be reversibly controlled by these methods. In this article, we reported a novel strategy that could enable the radical ring‐opening polymerization of macrocyclic allylic sulfides, wherein propagating specie is thiyl radical, to be controlled by reversible addition–fragmentation chain transfer (RAFT) agents. The key to the success of this strategy is the propagating thiyl radical can undergo desulfurization with isocyanide and generate a stabilized alkyl radical for reversible control. Systematic optimization of the reaction conditions allowed good control over the polymerization, leading to the formation of polymers with well‐defined architectures, exemplified by the radical block copolymerization of macrocyclic allylic sulfides and vinyl monomers and the incorporation of sequence‐defined segments into the polymer backbone. This work represents a significant step toward directly enabling the polymerizations of heteroatom‐centered radical propagation to be regulated by existing reversible‐deactivation radical polymerization techniques.

Chitosan Grafted with Thermoresponsive Poly(di(ethylene glycol) Methyl Ether Methacrylate) for Cell Culture Applications

Chitosan is a polysaccharide extracted from animal sources such as crab and shrimp shells. In this work, chitosan films were modified by grafting them with a thermoresponsive polymer, poly(di(ethylene glycol) methyl ether methacrylate) (PMEO2MA). The films were modified to introduce functional groups useful as reversible addition-fragmentation chain transfer (RAFT) agents. PMEO2MA chains were then grown from the films via RAFT polymerization, making the chitosan films thermoresponsive. The degree of substitution of the chitosan-based RAFT agent and the amount of monomer added in the grafting reaction were varied to control the length of the grafted PMEO2MA chain segments. The chains were cleaved from the film substrates for characterization using 1H NMR and a gel permeation chromatography analysis. Temperature-dependent contact angle measurements were used to demonstrate that the hydrophilic-hydrophobic nature of the film surface varied with temperature. Due to the enhanced hydrophobic character of PMEO2MA above its lower critical solution temperature (LCST), the ability of PMEO2MA-grafted chitosan films to serve as a substrate for cell growth at 37 °C (incubation temperature) was tested. Interactions with cells (fibroblasts, macrophages, and corneal epithelial cells) were assessed. The modified chitosan films supported cell viability and proliferation. As the temperature is lowered to 4 °C (refrigeration temperature, below the LCST), the grafted chitosan films become less hydrophobic, and cell adhesion should decrease, facilitating their removal from the surface. Our results indicated that the cells were detached from the films following a short incubation period at 4 °C, were viable, and retained their ability to proliferate.

Chain-Extendable Crosslinked Hydrogels Using Branching RAFT Modification.

Functional crosslinked hydrogels were prepared from 2-hydroxyethyl methacrylate (HEMA) and acrylic acid (AA). The acid monomer was incorporated both via copolymerization and chain extension of a branching, reversible addition-fragmentation chain-transfer agent incorporated into the crosslinked polymer gel. The hydrogels were intolerant to high levels of acidic copolymerization as the acrylic acid weakened the ethylene glycol dimethacrylate (EGDMA) crosslinked network. Hydrogels made from HEMA, EGDMA and a branching RAFT agent provide the network with loose-chain end functionality that can be retained for subsequent chain extension. Traditional methods of surface functionalization have the downside of potentially creating a high volume of homopolymerization in the solution. Branching RAFT comonomers act as versatile anchor sites by which additional polymerization chain extension reactions can be carried out. Acrylic acid grafted onto HEMA-EGDMA hydrogels showed higher mechanical strength than the equivalent statistical copolymer networks and was shown to have functionality as an electrostatic binder of cationic flocculants.

Covalent functionalization of Sb2S3 with poly(N-vinylcarbazole) for solid-state broadband laser protection.

An optimized complex multi-component nanomaterial system would help greatly enhance the optical limiting performance and applicability of 2D nanomaterials. By using antimony sulfide-[S-1-dodecyl-S'-(α,α'-dimethyl-α''-acetic acid)trithiocarbonate] (Sb2S3-DDAT) as a reversible addition fragmentation chain transfer (RAFT) agent, a highly soluble poly(N-vinylcarbazole)-covalently modified Sb2S3 (Sb2S3-PVK) was synthesized in situ and embedded into a non-optically active poly(methylmethacrylate) (PMMA) matrix producing a PMMA-based film with good optical quality. In contrast to both the Sb2S3/PMMA and Sb2S3:PVK blends/PMMA films, the Sb2S3-PVK/PMMA film exhibits more superior optical limiting performance. After annealing in N2 at 200 °C for 30 minutes, the achieved nonlinear absorption coefficient and limiting threshold are changed from 411.79 cm GW-1 and 1.93 J cm-2 at 532 nm and 242.79 cm GW-1 and 4.17 J cm-2 at 1064 nm before annealing to 478.04 cm GW-1 and 1.70 J cm-2 at 532 nm and 520.92 cm GW-1 and 1.40 J cm-2 at 1064 nm after annealing, respectively. These advantages make Sb2S3-PVK one of the potential promising candidates for a broadband laser protector in both the visible and near-infrared ranges.

Evaluation of allyl sulfides bearing methacrylate groups as addition-fragmentation chain transfer agents for low shrinkage dental composites

Polymerization shrinkage and the consequential shrinkage stress in methacrylate-based dental composites are crucial drawbacks for restorative dentistry. An effective way for the reduction of shrinkage stress is the incorporation of addition fragmentation chain transfer agents (AFCT agents). In this contribution, four novel polymerizable allyl sulfides were synthesized and evaluated in dental composites. Photo-DSC and DMTA measurements were performed to evaluate their influence on the polymerization rate and on the network homogeneity. Good to excellent shrinkage force values and mechanical properties were obtained for all AFCT based composites. Especially, the incorporation of AFCT agents containing multiple urethane and methacrylate moieties improved the mechanical properties. Hence, the incorporation of polymerizable and urethane-based allyl sulfides in dental composite is a promising strategy to obtain low shrinkage materials exhibiting high flexural strength and modulus.

Grafted polythiophene pendent polymer brushes and their electronanopatterning

• Nanolithography and patterning using polymer brushes with terthiophene pendents. • Terthiophene-containing chain transfer agent macroinitiator. • Nanolithography and patterning were done using conducting atomic force microscopy. • Nanopattern properties depend on the applied bias voltage and scan rate. Electrochemical nanolithography using grafted polymer brushes with terthiophene (3T) pendent was investigated. The film was fabricated by surface electropolymerization of a reversible addition−fragmentation chain-transfer agent macroinitiator containing a 3T pendant molecule and the subsequent polymer brush growth from a 3T functionalized methacrylate monomer (3T-Methacrylate). Electrochemical nanolithography and patterning were done using conducting atomic force microscopy (C-AFM) enabling precise nanopattern fabrication. In contrast to direct nanowriting, dip pen nanolithography, and nanolithographic additive manufacturing, the electrochemical nanolithography can be readily facilitated by applying a bias voltage between a conductive AFM tip and the grafted polymer brush film at ambient conditions and without ink transfer. The height and electrical resistance of the nanopatterns were dependent on the writing parameters (i.e. applied bias voltage and scan rate).

Reverse Sequence Polymerization‐Induced Self‐Assembly in Aqueous Media

We report a new aqueous polymerization-induced self-assembly (PISA) formulation that enables the hydrophobic block to be prepared first when targeting diblock copolymer nano-objects. This counter-intuitive reverse sequence approach uses an ionic reversible addition–fragmentation chain transfer (RAFT) agent for the RAFT aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA) to produce charge-stabilized latex particles. Chain extension using a water-soluble methacrylic, acrylic or acrylamide comonomer then produces sterically stabilized diblock copolymer nanoparticles in an aqueous one-pot formulation. In each case, the monomer diffuses into the PHPMA particles, which act as the locus for the polymerization. A remarkable change in morphology occurs as the ≈600 nm latex is converted into much smaller sterically stabilized diblock copolymer nanoparticles, which exhibit thermoresponsive behavior. Such reverse sequence PISA formulations enable the efficient synthesis of new functional diblock copolymer nanoparticles.

Lewis Pair RAFT Polymerization of Methacrylates on-Water: Evidence of Radical Propagation Mechanism

Abstract The Lewis pair (LP) composed of PPh3 and Cu(OTf)2 on-water is a newly emerging catalytic system for polymerization of polar vinyl monomers. Herein, we report the additive effect of the reversible addition–fragmentation chain transfer (RAFT) agents on the polymerization of six methacrylate monomers with various hydrophilicities. The polymerization control by the RAFT agents proved that this LP polymerization involves a radical propagating mechanism.

A Photoinduced Dual-Wavelength Approach for 3D Printing and Self-Healing of Thermosetting Materials.

Vat photopolymerization-based 3D printing techniques have been widely used to produce high-resolution 3D thermosetting materials. However, the lack of repairability of these thermosets leads to the production of waste. In this study, reversible addition fragmentation chain transfer (RAFT) agents are incorporated into resin formulations to allow visible light (405 nm) mediated 3D printing of materials with self-healing capabilities. The self-healing process is based on the reactivation of RAFT agent embedded in the thermosets under UV light (365 nm), which enables reformation of the polymeric network. The self-healing process can be performed at room temperature without prior deoxygenation. The impact of the type and concentration of RAFT agents in the polymer network on the healing efficiency is explored. Resins containing RAFT agents enable 3D printing of thermosets with self-healing properties, broadening the scope of future applications for polymeric thermosets in various fields.

A Photoinduced Dual‐Wavelength Approach for 3D Printing and Self‐Healing of Thermosetting Materials

AbstractVat photopolymerization‐based 3D printing techniques have been widely used to produce high‐resolution 3D thermosetting materials. However, the lack of repairability of these thermosets leads to the production of waste. In this study, reversible addition fragmentation chain transfer (RAFT) agents are incorporated into resin formulations to allow visible light (405 nm) mediated 3D printing of materials with self‐healing capabilities. The self‐healing process is based on the reactivation of RAFT agent embedded in the thermosets under UV light (365 nm), which enables reformation of the polymeric network. The self‐healing process can be performed at room temperature without prior deoxygenation. The impact of the type and concentration of RAFT agents in the polymer network on the healing efficiency is explored. Resins containing RAFT agents enable 3D printing of thermosets with self‐healing properties, broadening the scope of future applications for polymeric thermosets in various fields.

Bifunctional RAFT Agent Directed Preparation of Polymer/Graphene Oxide Composites.

Polymer/graphene oxide (GO) composites, which combine the physical properties of GO and the processability of polymers, are of increasing interest in a variety of applications ranging from conductive foams, sensors, to bioelectronics. However, the preparation of these composites through physical blending demands the polymers with functional groups that interact strongly with the GO. Here the design and synthesis of a new bifunctional reversible addition-fragmentation chain transfer (RAFT) agent are demonstrated, which allows the synthesis of polymers with predetermined molecular weights and low dispersibilities (Ð), while having functionalities at both polymer termini that allow strong binding to GO. To access polymers with diverse thermal and mechanical properties, acrylonitrile-styrene-acrylate (ASA) copolymers with different types of acrylates, both short and long side chains, are synthesized under the control of the bifunctional RAFT agent. Furthermore, the strong binding between GO and the synthesized polymers is verified and explored to prepare polymer/GO composites with diverse tensile strengths and conductivity in the range of semiconductors. Overall, this novel RAFT agent is expected to expand the utility of polymer/GO composites by providing well-defined polymers with tunable properties and strong binding with GO.

Polymerization shrinkage and shrinkage stress development in ultra-rapid photo-polymerized bulk fill resin composites

ObjectiveTo determine the polymerization shrinkage (%) and shrinkage stress (MPa) characteristics of ultra-rapid photo-polymerized bulk fill resin composites. MethodsTwo ultra-rapid photo-polymerized bulk fill (URPBF) materials: PFill and PFlow were studied, along with their comparators ECeram and EFlow. PFill contains an addition fragmentation chain transfer (AFCT) agent. The URPBR materials were irradiated using two different 3 s high irradiance protocols (3000 and 3200 mW/cm2 based on Bluephase PowerCure and VALO LCUs, respectively) and one 10 s standard protocol (1200 mW/cm2 based on a Bluephase PowerCure LCU). Bonded disk and Bioman II instruments were used to measure Polymerization shrinkage % and shrinkage stress MPa, respectively, for 60 min at 23 ± 1 °C (n = 5). Maximum shrinkage-rate and maximum shrinkage stress-rate were also calculated for 15 s via numerical differentiation. The data were analyzed via multiple One-way ANOVA and Tukey post-hoc tests (α = 0.05). ResultsPFill groups, regardless of their irradiance protocol, showed significantly lower PS than the comparator, ECeram (p < 0.05). However, PFlow irradiated via different protocols, was comparable to EFlow and ECeram (p > 0.05). PFill consistently produced stress results which were significantly lower than ECeram (p < 0.05) and were comparable for both high irradiance protocols (p > 0.05). PFlow only exhibited significantly higher shrinkage stress when polymerized with the 3 sVALO protocol (p < 0.05).The maximum shrinkage strain-rate (%/s) was significantly lower in PFill-10s and PFill-3s groups (using PowerCure LCU) compared to ECeram. However, no differences were seen between PFlow and EFlow (p > 0.05). The maximum shrinkage stress-rate of PFill and PFlow was comparable between different irradiation protocols, as well as to their comparator ECeram (p > 0.05). SignificanceHigh irradiation protocols over ultra-short periods led to slightly lower shrinkage strain but slightly higher stress, possibly due to reduced network mobility. The AFCT agent incorporated in PFill composite seemed to reduce shrinkage stress development, even with high irradiance protocols.

Asymmetric Colloidal Particles Fabricated by Polymerization-Induced Surface Self-Assembly Approach

In the past decades, the synthesis of asymmetric colloidal particles has been of wide concern in material science because of their anisotropic morphologies and unique properties. However, the synthesis of the asymmetric particles with controllable anisotropy still remains a big challenge because of the lack of effective methods. In this research, polymerization-induced surface self-assembly (PISSA) approach was demonstrated to be an effective method in the synthesis of colloidal particles with tunable asymmetric core–shell structures. Reversible addition–fragmentation chain transfer agents were covalently anchored onto the surfaces of silica particles and coupled onto the ends of methoxy polyethylene glycol (PEG) chains, leading to the synthesis of CTA-modified silica particles (SiO2-CTA) and PEG macro-CTA agents (PEG-CTA), respectively. PISSA process was conducted by using SiO2-CTA and PEG-CTA as co-RAFT agents in RAFT dispersion polymerization of styrene. In the RAFT polymerizations, polymer layers with PS nodules were formed on the surfaces of SiO2 particles. It was demonstrated that the formation of the nodules was related to the production of the PS homopolymer in the PISSA process. In order to control the asymmetric surface structures, RAFT dispersion polymerizations of styrene with added “free” RAFT agents were performed, and it turned out that the eccentrically positioned core–shell structures with silica cores and polymer layers were prepared. The colloidal particles experience morphology changes from surface nodules to snowman-like structures and finally to asymmetric spherical structures, depending on the monomer conversion and the feeding ratio of the co-RAFT agents. Kinetics studies were performed to investigate the mechanism of the formation of the asymmetric particles. After etching the silica cores with HF solution, asymmetric hollow capsules were fabricated.

Amphiphilic Block Copolymers with Vinyl Caprolactam as Kinetic Gas Hydrate Inhibitors

Macrosurfactants consisting of water-soluble poly(vinylcaprolactam) (PVCap) or poly(vinylpyrrolidone) (PVP) segments with comparatively shorter hydrophobic poly(styrene) (PS) or poly(2,3,4,5,6-pentafluorostyrene) (PPFS) segments were used as kinetic hydrate inhibitors (KHIs). These were synthesized with 2-cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)dithiocarbamate switchable reversible addition–fragmentation chain transfer (RAFT) agent at 60 °C or 90 °C for 1-P(S/PFS) or 1-PVCap, respectively, followed by chain extension at 90 °C or 70 °C with PVCap or PVP, respectively. The addition of PVCap to the pure methane-water system resulted in a 53% reduction of methane consumption (comparable to PVP with 51% inhibition) during the initial growth phase. A PS-PVCap block copolymer comprised of 10 mol% PS and 90 mol% PVCap improved inhibition to 56% compared to the pure methane-water system with no KHIs. Substituting PS with a more hydrophobic PPFS segment further improved inhibition to 73%. By increasing the ratio of the hydrophobic PS- to PVCap- groups in the polymer, an increase of its inhibition potential was measured. For PPFS-PVCap, an increase of PPFS ratio from 5% to 10% decreased the methane formation rate by 6%. However, PPFS-PVCap block copolymers with more than 20 mol% PPFS were unable to dissolve in water due to increase in hydrophobicity and the attendant low critical micelle concentration (CMC).

Surface Modification of Hypercrosslinked Vinylbenzyl Chloride PolyHIPEs by Grafting via RAFT

AbstractGrafting of glycidyl methacrylate from the surface of macroporous poly(4‐vinylbenzyl chloride‐co‐divinylbenzene) polyHIPEs (poly high internal phase emulsions) prepared by the polymerization of the continuous phase of high internal phase emulsions is performed. PolyHIPEs are hypercrosslinked using Friedel–Crafts reaction thus increasing specific surface area, and further functionalized with tris(2‐aminoethyl) amine. To the free amino groups reversible addition–fragmentation chain transfer (RAFT) agent 4‐cyano‐4‐[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid is immobilized and grafting is performed utilizing glycidyl methacrylate. Poly(glycidyl methacrylate) chains of ≈100 units in length are grafted onto the surface of the polyHIPEs. In comparison, non‐hypercrosslinked monoliths allow for substantially lower degree of immobilization of RAFT agent suggesting decreased accessibility of active sites on the polymer surface.

Synthesis of Amphiphilic Copolymers of Acrylic Acid and Styrene with the Desired Microstructure and Their Properties

The regularities of the controlled synthesis of amphiphilic copolymers of styrene and acrylic acid mediated by dithiobenzoate and trithiocarbonates as reversible addition fragmentation chain transfer agents in a 1,4-dioxane solution are considered. The influence of the general composition and chain microstructure on the dispersion stability and hydrodynamic sizes of polymer particles of copolymers containing from 40 to 90 mol % of acrylic acid units is studied. It is shown that in dilute aqueous media random copolymers are dispersed to individual compacted coils owing to the intrachain hydrophobic association of styrene units. The addition of two poly(acrylic acid) blocks to such a copolymer improves its dispersibility in water, and the attachment of two polystyrene blocks makes it insoluble in water because of the interchain association of polystyrene units. The synthesized copolymers possess surface activity, and when applied to a hydrophilic glass surface, they moderately hydrophobize it. In general, this synthetic approach opens up broad prospects for obtaining a wide range of new polymer macromolecules with different properties from one pair of traditional monomers.

Effect of Chain-End Chemistries on the Efficiency of Coupling Antibodies to Polymers Using Unnatural Amino Acids.

Novel conjugates that incorporate strategies for increasing the therapeutic payload, such as targeted polymeric delivery vehicles, have great potential in overcoming limitations of conventional antibody therapies that often exhibit immunogenicity and limited drug loading. Click chemistry has significantly expanded the toolbox of effective strategies for developing hybrid polymer-biomolecule conjugates, however, effective systems require orthogonality between the polymer and biomolecule chemistries to achieve efficient coupling. Here, three cycloaddition-based strategies for antibody conjugation to polymeric carriers are explored and show that a purely radical-based method for polymer synthesis and subsequent biomolecule attachment has a trade-off between coupling efficiency of the antibody and the ability to synthesize polymers with controlled chemical properties. It is shown that careful consideration of both coupling chemistries as well as the potential effect of how this modulates the chemical properties of the polymer nanocarrier should be considered during the development of such systems. The strategies described offer insight into improving conjugate development for therapeutic and theranostic applications. In this system, polymerization using conventional and established reversible addition fragmentation chain transfer (RAFT) agents, followed by multiple post-modification steps, always leads to systems with more defined chemical architectures compared to strategies that utilize alkyne-functional RAFT agents.