Addition-fragmentation Chain Transfer Agent Research Articles

Thiocarbonyls as Performance Enhancing Additives for Lithium-Sulfur Batteries

The lithium-ion battery (LIB) has been key to the electrification of the automotive sector. It is anticipated that electrification of sectors such as haulage and aerospace will require energy storage systems with capacities and performance beyond the capabilities of traditional LIB chemistries.[1] Lithium-sulfur (Li-S) batteries are a front-runner among next generation battery technologies, thanks to their high theoretical capacities (1675 mAh g-1) and impressive gravimetric energy densities (2,700 Wh kg-1).[2,3] Despite their potential, there are numerous chemical challenges (active material dissolution, polysulfide shuttle, dendrite formation etc.) that must be overcome before widespread adoption of the technology.[4] Electrolyte additives have been explored as a means to minimise active material loss within the cell and improve long-term cyclability and cell discharge capacity.[5]Thiocarbonyl compounds are well known in the polymer science community, behaving as reversible addition fragmentation chain transfer (RAFT) agents.[6] The reactivity of the thiocarbonyl group in the presence of nucleophilic molecules such as polysulfides renders them promising additives for Li-S batteries. Here, we present our studies on ethyl 2-(4-methoxyphenylcarbonothioyl thio)acetate (EM), a thiocarbonyl derivative, as a new type of electrolyte additive that can improve the cycle life of Li-S batteries. A variety of electrochemical and analytical techniques, combined with computational density functional theory (DFT) calculations, have been employed to assess the suitability of EM as an additive in Li2S cells. We have built an understanding of its interactions with active materials in a Li-S cell, with results proving that EM chemically reacts with and aids the oxidation of Li2S. Galvanostatic cycling has allowed us to corroborate our electrochemical and computational findings with cell cycling performance. We observe a significant enhancement in long-term cycling capacity when the additive is introduced to the electrolyte. Figure 1. A blot plot displaying the discharge capacities at specific cycle numbers for standard (light grey) and EM (dark grey) cells to provide a statistical comparison.

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.

Branched polymer grafted graphene oxide (GO) as a 2D template for calcium phosphate growth

HypothesisGraphene Oxide (GO)-templated deposition of inorganic materials through synthesis on dispersed single sheets of GO is often complicated by the loss of the desired 2D morphology owing to the coagulation of GO sheets at high salt concentrations and non-templated homogenous nucleation. Modifying GO with anionic polymer is expected to solve both problems by i) enhancing electrostatic(steric) stabilization upon exposure to high concentrations of the ionic precursors, and ii) offering additional nucleation sites at the grafted anionic moieties to avoid homogeneous secondary nucleation. ExperimentsGO was grafted with branched copolymers of poly(ethylene glycol) methacrylate (PEGMA 500) and diethylene glycol dimethacrylate (DEGDMA) and ω-vinyl terminated methacrylic acid macromonomer (P(MAA)), the latter serving as an addition-fragmentation chain transfer agent. The colloidal stability of GO dispersions in water toward salt was evaluated before and after modification. Precipitation of calcium phosphate (CaP) was performed by incubating modified GO in the precursor solutions. The conditions were optimized to maximize the nucleation selectively onto GO without homogeneous CaP nucleation and coagulation of the GO-sheets. FindingsThe copolymer grafted GO-sheets shows superior colloidal stability when dispersed in water. No aggregation occurs in the incubating ionic CaP precursor solutions. The optimum templated deposition of CaP onto the GO sheets by precipitation is to add a second shot of precursors after the nucleation stage to obtain GO sheets fully decorated with calcium phosphate nanorods without self-nucleation. Via the careful design on the GO modification and incubation process, the growth of calcium phosphate nanorods were confined in the desired 2D order exclusively, hereby achieving the goal of an efficient GO-templated synthesis.

Versatile morphology transition of nano-assemblies via ultrasonics/microwave assisted aqueous polymerization-induced self-assembly based on host–guest interaction

Nano-assemblies have wide applications in biomedicine, functional coatings, Pickering emulsifiers, hydrogels, and so forth. The preparation of assemblies mainly utilizes the polymerization-induced self-assembly (PISA) method, which can produce high-concentration nanoscale assemblies in one step. However, the initiation processes of most reported PISA are limited to thermal initiation. Here, we reported two green and efficient methods for synthesizing nano-assemblies with various morphologies using ultrasound (20 kHz)/ microwave (500 W) assisted aqueous-phase RAFT-PISA in 3 h and 1 h. Cyclodextrin (CD) and styrene (St) nucleating monomer were complexed in a 1:1 ratio. Then, using Poly (ethylene glycol) methyl ether as the macromolecular reversible addition-fragmentation chain transfer (RAFT) agent (PEG-CTA) to control the CD/St complexes, the conversion rate of St monomer was respectively 27 %–60 %, 20 %–30 % within 3 h and 1 h under ultrasonics/microwave assisted PISA. Results showed that the morphologies of the assemblies are not only related to the length of PS block, but also to the assistance types and the remaining monomer concentration. The results showed that only PEG45-b-PS90 and PEG45-b-PS241 assemblies prepared by ultrasonics assisted PISA form evolved lamellaes and vesicles (100 nm), which break through the limitation of kinetic freezing. But the ultrasonic reaction on morphology of assemblies is not all favourable. For one thing, it can promote the movement of particles; for another, it makes reverse morphology transformation and sphere is preferred morphology. Therefore, the main reason of morphology evolution is the remaining monomer concentration of PEG45-b-PS90 and PEG45-b-PS241 assemblies reaches to 55 %–65 %, which promoting the segment movement. The results showed that the morphology of the assemblies prepared by microwave assisted PISA changed from spherical micelles to short rods, and finally to vesicles (120–140 nm) as the length of hydrophobic PS block increases. The kinetic freezing problem was solved in microwave-assisted PISA due to the action of microwaves and more remaining monomer concentration. Both them can boost particles movement.

Preparation of diblock copolymer nano-assemblies by ultrasonics assisted ethanol-phase polymerization-induced self-assembly

Assemblies are widely used in biomedicine, batteries, functional coatings, Pickering emulsifiers, hydrogels, and luminescent materials. Polymerization-induced self-assembly (PISA) is a method for efficiently preparing particles, mainly initiated thermally. However, thermally initiated PISA usually requires a significant amount of time and energy. Here, we demonstrate the preparation of nano-assemblies with controllable morphologies and size using ultrasound (20 kHz) assisted ethanol-phase RAFT-PISA in three hours. Using poly (N, N-dimethylaminoethyl methacrylate) as the macromolecular reversible addition-fragmentation chain transfer agent (PDMA-CTA) to control the nucleating monomer benzyl methacrylate (BzMA), we obtained nano-assemblies with different morphologies. With the length of hydrophobic PBzMA block growth, the morphologies of the assemblies at 15 wt% solid content changed from spheres to vesicles, and finally to lamellae; the morphologies of the assemblies at 30 wt% changed from spheres micelles to short worms, then vesicles, and finally to large compound vesicles. With the same targeted degree of polymerization, nano-assemblies having a 30 wt% solid content display a more evolved morphology. The input of ultrasonic energy makes the system have higher surface free energy, results the mass fraction interval of solventphilic blocks (fhydrophilic) corresponding to the formation of spherical micelles is expanded from fhydrophilic > 45 % to fhydrophilic > 31 % under ultrasound and the fhydrophilic required to form worms, vesicles, and large composite vesicles decreases in turn. It is worth noting that the fhydrophilic interval of worms prepared by ultrasonics assisted PISA gets larger. Overall, the highly green, externally-regulatable and fast method of ultrasonics assisted PISA can be extended to vastly different diblock copolymers, for a wide range of applications.

Impact of a poly(ethylene glycol) corona block on drug encapsulation during polymerization induced self-assembly.

Polymerization induced self-assembly (PISA) provides a facile platform for encapsulating therapeutics within block copolymer nanoparticles. Performing PISA in the presence of a hydrophobic drug alters both the nanoparticle shape and encapsulation efficiency. While previous studies primarily examined the interactions between the drug and hydrophobic core block, this work explores the impact of the hydrophilic corona block on encapsulation. Poly(ethylene glycol) (PEG) and poly(2-hydroxypropyl methacrylate) (PHPMA) are used as the model corona and core blocks, respectively, and phenylacetic acid (PA) is employed as the model drug. Attachment of a dithiobenzoate end group to the PEG homopolymer - transforming it into a macroscopic reversible addition-fragmentation chain transfer agent - causes the polymer to form a small number of nanoscopic aggregates in solution. Adding PA to the PEG solution encourages further aggregation and macroscopic phase separation. During the PISA of PEG-PHPMA block copolymers, inclusion of PA in the reaction mixture promotes faster nucleation of spherical micelles. Although increasing the targeted PA loading from 0 to 20 mg mL-1 does not affect the micelle size or shape, it alters the drug spatial distribution within the PISA microenvironment. PA partitions into either PEG-PHPMA micelles, deuterium oxide, or other polymeric species - including PEG aggregates and unimer chains. Increasing the targeted PA loading changes the fraction of drug within each encapsulation site. This work indicates that the corona block plays a critical role in dictating drug encapsulation during PISA.

Unique Polymer-Stabilized Liquid Crystal Structure Prepared by Addition of a Reversible Addition-Fragmentation Chain Transfer Agent.

Polymer-stabilized liquid crystals (PSLCs) are important electrically switchable materials due to their superior electro-optical properties. Nevertheless, it remains a formidable challenge to balance PSLCs' instant electro-optical performance and long-term durability due to their relatively low polymer content and the related sensitivity to external force. Herein, we demonstrate the possibility of regulating the polymer network structure in PSLCs via reversible addition-fragmentation chain transfer (RAFT) polymerization reactions of acrylate monomers with a chain transfer agent (CTA). By controlling the concentration of CTA and conditions of photopolymerization, the kinetics of the polymerization reaction can be modified. Compared to conventional free-radical (FR) polymerization, the reduced chain growth rate leads to sufficient chain relaxation, reorientation of liquid crystal (LC) directors, and alleviation of shrinkage stresses in the RAFT polymerization process. This in turn produces an ordered polymer network structure in the vertical direction and a uniform distribution in the horizontal plane. As a result, the PSLC network presents increased elasticity with a lower hysteresis effect and greatly improved durability. Our research offers insightful guidance for the fine-tuning of polymer network structures to prepare advanced LC/polymer composite structures with outstanding performances.

Tailoring highly stable anion exchange membranes with graft molecular structure ordering using reversible addition-fragmentation chain transfer polymerization for alkaline fuel cells

The radiation-induced grafting is used to prepare a variety of anion-exchange membranes (AEM) based on poly(ethylene-co-tetrafluoroethylene) (ETFE) utilizing a reversible addition-fragmentation chain transfer (RAFT) agent. The copolymerization process is controlled by the RAFT agent, resulting in AEMs with a restricted molecular weight dispersion. As a result, RAFT-AEMs exhibit decreased water uptake and reduced swelling. A significant improvement in thermal and mechanical characteristics is evidenced, while the conductivity remains practically unaltered. Anion-exchange membrane fuel cell (AEMFC) tests revealed that conventional RIG-AEMs and RAFT-AEMs with low RAFT content (5 wt%) have comparable beginning-of-life performances (∼0.95 W cm−2). However, for higher RAFT contents, the performance trends to decrease indicating an imbalance in water management. Furthermore, short-term stability tests suggest that RAFT-AEMs are able to operate highly stable, with a conductivity rate loss of 0.05% h−1, which represents an improvement of 160% in comparison to conventional RIG-AEM. AFM analysis demonstrated that structural ordering molecular and morphology tailor the fundamental properties of ETFE-based AEMs, combining enhanced performance and stability for alkaline fuel cell applications.

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

The 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.

Kinetic Modeling of the Synthesis of Poly(4-vinylpyridine) Macro-Reversible Addition-Fragmentation Chain Transfer Agents for the Preparation of Block Copolymers

Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most common controlled polymerization techniques to prepare well-defined, rather narrow dispersed polymers due to reduced demands in reactant preparation. Despite these advantages, RAFT polymerization was so far primarily utilized on small laboratory scales. This study presents a first step to a scaled-up RAFT polymerization by developing and experimentally validating a kinetic model on the example of the polymerization of 4-vinylpyridine (4VP), which to date is not described in the literature. With the implementation of the results from modeling, the synthesis process was extended to a medium scale (from 6 to 36 g), while the same high conversions, molar mass, and low dispersity as in the smaller scale were achieved. The process is also optimized regarding the high degree of livingness necessary for using the 4VP polymers as a macro-RAFT agent in the subsequent reaction step for the synthesis of poly(4-vinylpyridine)-b-polystyrene diblock copolymers by RAFT dispersion polymerization.

Fabrication of a Molecularly-Imprinted-Polymer-Based Graphene Oxide Nanocomposite for Electrochemical Sensing of New Psychoactive Substances

As new psychoactive substances (commonly known as "the third generation drugs") have characteristics such as short-term emergence, rapid updating, and great social harmfulness, there is a large gap in the development of their detection methods. Herein, graphite oxide (GO) was first prepared and immobilized with a reversible addition-fragmentation chain transfer (RAFT) agent, then a new psychoactive substance (4-MEC) was chosen as a template, and then the surface RAFT polymerization of methacrylamide (MAAM) was carried out by using azobisisobutyronitrile (AIBN) as an initiator and divinylbenzene (DVB) as a cross-linker. After the removal of the embedded template, graphene oxide modified by molecularly imprinted polymers (GO-MIPs) was finally obtained. Owing to the specific imprinted cavities for 4-MEC, the satisfactory selectivity and stability of the GO-MIP nanocomposite have been demonstrated. The GO-MIP nanocomposite was then used to fabricate the electrochemical sensor, which displayed a high selectivity in detecting 4-MEC over a linear concentration range between 5 and 60 μg mL-1 with a detection limit of 0.438 μg mL-1. As a result, the GO-MIPs sensor developed an accurate, efficient, convenient, and sensitive method for public security departments to detect illicit drugs and new psychoactive substances.

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.

Activity Improvement and Thermal Stability Enhancement of D-Aminoacylase Using Protein-Polymer Conjugates

In this study, the synthesis of new polymer-protein conjugates using a grafting-from strategy was performed by employing photo-induced electron transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. D-aminoacylase is an industrially significant enzyme for the preparation of chiral amino acids and it is coupled with reversible addition-fragmentation (RAFT) chain transfer agent (CTA) using activated ester chemistry. The effects of polymeric side chain compositions on the activity of D-aminoacylase were studied with two different polymeric side chain lengths. For this reason, two monomers, a hydrophilic N-(2-aminoethyl acrylamide) and a hydrophobic and N- (iso-butoxymethyl) acrylamide were used, respectively. It was found that modification by grafting from strategy increased the thermal stability of D-aminoacylase enzyme. Additionally, the hydrophobic monomer conjugate has been reported to increase the activity of the enzyme more than the hydrophilic monomer.

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.

Fluorinated reversed micelles by polymerization-induced self-assembly with main-chain-type semifluorinated alternating copolymer

In this work, based on the semifluorinated macro-RAFT (reversible addition-fragmentation chain transfer) agent and polymerization-induced self-assembly (PISA) strategy, we established a mild and facile method to prepare reversed micelles up to 40 wt% of solid content with main-chain-type semifluorinated alternating copolymer as shell and hydrophilic polymer as core for the first time. The fluorinated macro-RAFT agent was synthesized by combination of step transfer-addition & radical-termination (START) polymerization and post-modification method. The reversed micelles were generated by the PISA of N,N-dimethacrylamide (DMA) in the presence of the fluorinated macro-RAFT agent in the non-polar solvent toluene at 70 °C, and fluorinated reversed micelles can be fixed in the presence of crosslinker ethyleneglycol dimethacrylate (EGDMA). This strategy will facilitate to open a new way in designing novel functional synthetic fluorinated nanomaterials.

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.

Linear and Star Block Copolymer Nanoparticles Prepared by Heterogeneous RAFT Polymerization Using an ω,ω-Heterodifunctional Macro-RAFT Agent.

Herein, an ω,ω-heterodifunctional macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agent containing two different RAFT end groups was synthesized and employed to mediate aqueous photoinitiated RAFT dispersion polymerization of a methacrylic monomer. Because of the different RAFT controllability of two RAFT end groups toward methacrylic monomers, the RAFT end group with good controllability dominated the polymerization while the other RAFT end group with poor controllability was unreacted, leading to the formation of linear block copolymers. Because of the unique structure of the linear block copolymers, a diverse set of block copolymer nanoparticles with rich RAFT groups at the interface of the hydrophilic corona/the hydrophobic core were successfully prepared. Finally, μ-A(BC)C miktoarm star block copolymer nanoparticles were prepared by RAFT seeded emulsion polymerization of an acrylic monomer, which enables the further morphological control over polymer nanoparticles. We believe that the utilization of an ω,ω-heterodifunctional macro-RAFT agent in heterogeneous RAFT polymerization will offer considerable opportunities for the rational synthesis of well-defined molecular architectures and polymer nanoparticles.

Dithiocarbamates as Effective Reversible Addition-Fragmentation Chain Transfer Agents for Controlled Radical Polymerization of 1-Vinyl-1,2,4-triazole.

Narrow dispersed poly(1-vinyl-1,2,4-triazole) (PVT) was synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization of 1-vinyl-1,2,4-triazole (VT). AIBN as the initiator and dithiocarbamates, xanthates, and trithiocarbonates as the chain transfer agents (CTA) were used. Dithiocarbamates proved to be the most efficient in VT polymerization. Gel permeation chromatography was used to determine the molecular weight distribution and polydispersity of the synthesized polymers. The presence of the CTA stabilizing and leaving groups in the PVT was confirmed by 1H and 13C NMR spectroscopy. The linear dependence of the degree of polymerization on time confirms the conduct of radical polymerization in a controlled mode. The VT conversion was over 98% and the PVT number average molecular weight ranged from 11 to 61 kDa. The polydispersity of the synthesized polymers reached 1.16. The occurrence of the controlled radical polymerization was confirmed by monitoring the degree of polymerization over time.

Metal scavenging resin tethered with catechol or gallol binders via reversible addition–fragmentation chain transfer polymerisation

Resin-supported metal scavengers are interesting in the separation and purification of target organic compounds and solvents because they avail a suitable and facile material platform for the adsorption of metal ions, thus enabling successive recycling. Here, a mussel-inspired catechol-functionalised or tunicate-inspired gallol-functionalised polymer, which was tethered to the Merrifield resin containing self-reducing hydroxyl groups that could bind well with metal ions, was synthesised via reversible addition–fragmentation chain transfer polymerisation. The number of functional groups on the surface of the resin was quantitatively controlled by modulating the ratio of the monomer to the resin-attached chain transfer agent. The metal ion adsorption capacity, as well as removal ability of the resin in an aqueous solution, which increased with the increasing number of the dihydroxy and trihydroxy groups, was investigated employing silver, copper, zinc, magnesium, lead, and iron ions. The polytrihydroxystyrene-bearing resin exhibited better metal ion-scavenging performance compared with the polydihydroxystyrene-incorporated resin at the same grafting degree in an aqueous solution owing to the tridentate structure of the gallol group, which acted as a ligand in the synthesis of the metal complex. The developed resins demonstrated that the residual metal catalyst that was derived from synthesising the conjugated polymer can be successfully removed. • Polydihydroxystyrene (PDHS) or polytrihydroxystyrene (PTHS) was incorporated into microbeads. • Reversible addition-fragmentation chain transfer agents afforded mussel-inspired catechol or tunicate-inspired gallol groups. • Hydroxyl group-containing polymers were synthesised on commercial resins to avail many metal-ion-binding sites. • The successive adsorption/desorption of metals from the PDHS or PTHS-immobilised resins demonstrated its reusability. • The metal scavenger resin was used to remove the Cu catalyst after the click reaction of the block copolymers.