Reversible Addition-fragmentation Chain Transfer Research Articles

Peculiar Behavior of Methyl Methacrylate Emulsion Polymerization-Induced Self-Assembly Mediated by RAFT Using Poly(Methacrylic Acid) Macromolecular Chain Transfer Agent.

Reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of methyl methacrylate (MMA) is successfully performed in water in the presence of a poly(methacrylic acid) (PMAA) macromolecular chain transfer agent (macroCTA) leading to the formation of self-stabilized PMAA-b-PMMA amphiphilic block copolymer particles. At pH3.7, the reactions are well-controlled with narrow molar mass distributions. Increasing the initial pH, particularly above 5.6, results in a partial loss of reactivity of the PMAA macroCTA. The effect of the degree of polymerization (DPn) of the PMMA block, the solids content, the nature of the hydrophobic segment, and the pH on the morphology of the obtained diblock copolymer particles is then investigated. Worm-like micelles are formed for a DPn of PMMA of 20 (PMMA20), while "onion-like" particles and spherical vesicles are obtained for PMMA30 and PMMA50, respectively. In contrast, spherical particles are obtained for the DPns higher than 150. This unusual evolution of particle morphologies upon increasing the DPn of the PMMA block seems to be related to hydrogen bonds between hydrophilic MAA and hydrophobic MMA units.

Biocompatible polyethersulfone membrane modified by hydrophilic polymer decorated magnetic nanoparticles gilded by facile external magnetic field

AbstractPolymer‐based membranes such as polyethersulfone are widely used for hemodialysis and bio‐related applications; however, this type of membrane still fails to satisfy optimum performance in terms of clearance, safety, and bio‐adaptability. Herein, a polymer brush of polyvinylpyrrolidone is decorated on the surface of magnetic nanoparticles by using reversible addition‐fragmentation chain transfer polymerization (RAFT), and under the guidance of an external magnetic field, the prepared magnetic nanoparticles with the polymer brush system are blended with a polyethersulfone membrane during a liquid‐liquid phase inversion process. The prepared membranes with different loads of the pure magnetic nanoparticle and polyvinylpyrrolidone@magnetic nanoparticle polymer brushes are prepared, compared with the pristine membrane, the modified membrane shows a high flux value at 349 L m−2 h−1 and 99.9% bovine serum albumin protein rejection. This membrane also demonstrated improved hydrophilicity and pore structure compared with the pristine membrane. Concerning the blood biocompatibility analysis, the modified membranes acquire prolonged time for clotting factors such as prothrombin time, activated partial thromboplastin time, and thrombin time while exhibiting less fibrinogen concertation at 0.4 g L−1. Furthermore, for the first time, an innovative method for fouling detection based on magnetic field attenuation due to protein accumulation on the membrane surface is reported; the method in this work could be a positive booster for the safe use of polymeric membranes in hemodialysis and bio‐based applications.

Pyrazino[2,3-f][1,10]phenanthroline Derivatives as Robust Photocatalysts Enabling ppm-Level Organocatalyzed Photoinduced Electron/Energy Transfer Reversible Addition–Fragmentation Chain Transfer Polymerization

Pyrazino[2,3-<i>f</i>][1,10]phenanthroline Derivatives as Robust Photocatalysts Enabling ppm-Level Organocatalyzed Photoinduced Electron/Energy Transfer Reversible Addition–Fragmentation Chain Transfer Polymerization

Four-Component Statistical Copolymers by RAFT Polymerization

This manuscript serves as the starting point for in-depth research of multicomponent, statistical, methacrylate-based copolymers that potentially mimic the behavior of proteins in aqueous solutions. These synthetic macromolecules are composed of specially chosen comonomers: methacrylic acid (MAA), oligoethylene glycol methyl ether methacrylate (OEGMA475), 2-(dimethylamino)ethyl methacrylate (DMAEMA) and benzyl methacrylate (BzMA). Monomer choice was based on factors such as the chemical nature of pendant functional groups, the polyelectrolyte/polyampholyte and amphiphilic character and the overall hydrophobic–hydrophilic balance (HLB) of the obtained quaterpolymers. Their synthesis was achieved via a one-pot reversible addition fragmentation chain transfer (RAFT) polymerization in two distinct compositions and molecular architectures, linear and hyperbranched, respectively, in order to explore the effects of macromolecular topology. The resulting statistical quaterpolymers were characterized via 1H-NMR and ATR-FTIR spectroscopies. Their behavior in aqueous solutions was studied by dynamic (DLS) and electrophoretic light scattering (ELS) and fluorescence spectroscopy (FS), producing vital information concerning their self-assembly and the structure of the formed aggregates. The physicochemical studies were extended by tuning parameters such as the solution pH and ionic strength. Finally, the quaterpolymer behavior in FBS/PBS solutions was investigated to test their colloid stability and biocompatibility in an in vivo-mimicking, biological fluid environment.

Preparation of a Molecularly Imprinted Polymer on Polyethylene Terephthalate Platform Using Reversible Addition-Fragmentation Chain Transfer Polymerization for Tartrazine Analysis via Smartphone

This work describes the preparation of a molecularly imprinted polymer (MIP) platform on polyethylene terephthalate (MIP-PET) via RAFT polymerization for analyzing tartrazine using a smartphone. The MIP-PET platform was characterized using Fourier transform infrared (FTIR) techniques, Raman Spectroscopy, X-ray photoelectron spectroscopy (XPS), and confocal microscopy. The optimal pH and adsorption time conditions were determined. The adsorption capacity of the MIP-PET plates with RAFT treatment (0.057 mg cm−2) was higher than that of the untreated plates (0.028 mg cm−2). The kinetic study revealed a pseudo-first-order model with intraparticle diffusion, while the isotherm study indicated a fit for the Freundlich model. Additionally, the MIP-PET demonstrated durability by maintaining its adsorption capacity over five cycles of reuse without significant loss. To quantify tartrazine, images were captured using a smartphone, and the RGB values were obtained using the ImageJ® free program. A partial least squares regression (PLS) was performed, obtaining a linear range of 0 to 7 mg L−1 of tartrazine. The accuracy of the method was 99.4% (4.97 ± 0.74 mg L−1) for 10 samples of 5 mg L−1. The concentration of tartrazine was determined in two local soft drinks (14.1 mg L−1 and 16.5 mg L−1), with results comparable to the UV–visible spectrophotometric method.

Synthesis of Thermoresponsive Chitosan-graft-Poly(N-isopropylacrylamide) Hybrid Copolymer and Its Complexation with DNA

A hybrid synthetic-natural, thermoresponsive graft copolymer composed of poly(N-isopropyl acrylamide) (PNIPAM) side chains, prepared via RAFT polymerization, and a chitosan (Chit) polysaccharide backbone, was synthesized via radical addition-fragmentation reactions using the “grafting to” technique, in aqueous solution. ATR-FTIR, TGA, polyelectrolyte titrations and 1H NMR spectroscopy were employed in order to validate the Chit-g-PNIPAM copolymer chemical structure. Additionally, 1H NMR spectra and back conductometric titration were utilized to quantify the content of grafted PNIPAM side chains. The resulting graft copolymer contains dual functionality, namely both pH responsive free amino groups, with electrostatic complexation/coordination properties, and thermoresponsive PNIPAM side chains. Particle size measurements via dynamic light scattering (DLS) were used to study the thermoresponsive behavior of the Chit-g-PNIPAM copolymer. Thermal properties examined by TGA showed that, by the grafting modification with PNIPAM, the Chit structure became more thermally stable. The lower critical solution temperature (LCST) of the copolymer solution was determined by DLS measurements at 25–45 °C. Furthermore, dynamic and electrophoretic light scattering measurements demonstrated that the Chit-g-PNIPAM thermoresponsive copolymer is suitable of binding DNA molecules and forms nanosized polyplexes at different amino to phosphate groups ratios, with potential application as gene delivery systems.

Enhanced performance in lithium metal batteries: A dual-layer solid electrolyte interphase strategy via perfluoropolyether derivative additive

The utilization of metallic lithium at the negative electrode is regarded as the most promising approach to enhance the energy density of current lithium battery systems. However, uncontrolled lithium dendrite growth leading to instability and low coulombic efficiency (CE) hinders the practical application of metallic lithium as the negative electrode. This study unveils the synthesis of a perfluoropolyether (PFPE) derivative electrolyte additive, denoted as PPP, through reversible addition-fragmentation chain transfer (RAFT) polymerization involving 2-butylsulfanyl-thiocarbonylsulfanyl-propionic acid (PABTC), PFPE and polydioxolane acrylate (PDXLA) as precursors. This additive incorporates fluorinated segments to enhance lithium ion transport efficiency, along with organic segments to improve battery stability. It facilitates the formation of a distinctive dual-layered solid electrolyte interphase (SEI) in 1,3-dioxolane (DOL) based lithium metal batteries. The upper organic protective layer mitigates volume deformation and suppresses lithium dendrite growth, while the lower dense LiF layer enhances lithium ion transport rates, thus improving battery performance. The resulting dual-layer SEI structured LFP | DOL-PPP | Li cell exhibits a capacity retention of 94.1 % after 150 cycles. Moreover, the Li | DOL-PPP | Li cell demonstrates stable cycling performance exceeding 1800 h at 0.2 mA cm-2. This work underscores the significant potential of PFPE derivatives as electrolyte additives in the design and optimization of lithium batteries.

Unravelling Competitive Interactions between Polymer Side Chains and End Groups with β-Cyclodextrin.

This study investigates unexpected competitive host-guest interactions of β-cyclodextrin which can occur with polymers in aqueous solution, using the examples of the two polymers poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) and poly(glycerol mono methacrylate) (PGMA). Systematic structural modifications of the polymer provide insight into the host-guest interaction with β-cyclodextrin and the competition between side chains and end groups such as hydrophobic end groups remaining from reversible addition fragmentation chain transfer (RAFT) polymerization or intentionally implemented molecular recognition units such as arylazopyrazole (AAP) photoswitches. This article is protected by copyright. All rights reserved.

Block and Statistical Copolymers of Methacrylate Monomers with Dimethylamino and Diisopropylamino Groups on the Side Chains: Synthesis, Chemical Modification and Self-Assembly in Aqueous Media.

The synthesis of amphiphilic diblock and statistical (random) copolymers of poly(dimethylamino ethyl methacrylate) and poly((2-(diisopropylamino) ethyl methacrylate) using the reversible addition-fragmentation chain transfer polymerization technique (RAFT polymerization) is reported. The precursor copolymers were chemically modified to create derivative copolymers of polyelectrolyte and polyampholyte nature with novel solution properties. Moreover, their molecular and physicochemical characteristics, as well as their self-assembly in aqueous media as a function of molecular architecture and composition, are investigated by using size exclusion chromatography, spectroscopic characterization techniques and light scattering techniques. Furthermore, the behavior and properties of the obtained micelles and aggregates were studied, depending on the pH, temperature and ionic strength of the aqueous solutions. The response of the systems to changes in these parameters shows interesting behavior and new properties that are useful for their utilization as nanocarriers of pharmaceutical compounds.

Antiviral Activities of Heparan Sulfate Mimetic RAFT Polymers Against Mosquito-borne Viruses.

Mosquito-borne viruses are a major worldwide health problem associated with high morbidity and mortality rates and significant impacts on national healthcare budgets. The development of antiviral drugs for both the treatment and prophylaxis of these diseases is thus of considerable importance. To address the need for therapeutics with antiviral activity, a library of heparan sulfate mimetic polymers was screened against dengue virus (DENV), Yellow fever virus (YFV), Zika virus (ZIKV), and Ross River virus (RRV). The polymers were prepared by RAFT polymerization of various acidic monomers with a target MW of 20 kDa (average Mn ∼ 27 kDa by GPC). Among the polymers, poly(SS), a homopolymer of sodium styrenesulfonate, was identified as a broad spectrum antiviral with activity against all the tested viruses and particularly potent inhibition of YFV (IC50 = 310 pM). Our results further uncovered that poly(SS) exhibited a robust inhibition of ZIKV infection in both mosquito and human cell lines, which points out the potential functions of poly(SS) in preventing mosquito-borne viruses associated diseases by blocking viral transmission in their mosquito vectors and mitigating viral infection in patients.

Multiresponsive Behavior of the Pickering Emulsifier and Its Application for Collecting Small Oil Droplets in Water.

Responsive Pickering emulsions, with unique nanoparticle interfaces and sensitivity to external stimuli, significantly enhanced the stability and applicability of Pickering emulsions. Multifunctional composite material poly((2-(dimethylaminoethyl methacrylate)-b-(acrylate cyclodextrin))/Fe3O4 nanoparticles, namely P(DMAEMA-b-A-CD)/Fe3O4, with both multiresponsive characteristics and emulsifying capabilities had been designed to remove small oil droplets from water. Using the reversible addition-fragmentation chain transfer (RAFT) method, diblock polymers P(DMAEMA-b-A-CD) were grown in a controlled manner on the surface of Fe3O4. The Fe3O4 core showed responsiveness to a magnetic field, and the block copolymers prepared via the RAFT method demonstrated reactivity to both pH and CO2. The P(DMAEMA-b-A-CD)/Fe3O4 nanoparticles exhibited the capability to form Pickering/Oxford emulsions with exceptional stabilization properties. It could be observed that the introduction of CO2, acid, and a magnetic field led to the breakage of the emulsion, while the emulsion could be restabilized by removing the CO2 and the magnetic field or by adding alkali. Measurements of interfacial tension, ζ-potential, and contact angle demonstrated that the emulsification/breakdown mechanisms associated with pH and CO2/N2 were related to the surface wettability of the nanoparticles. In addition, the emulsifier had an excellent cycling capacity with at least 10 cycles by CO2/N2. Additionally, P(DMAEMA-b-A-CD)/Fe3O4 nanoparticles exhibited excellent stability in oil phases with large polarity differences and various real oil phases with different viscosities. Importantly, the P(DMAEMA-b-A-CD)/Fe3O4 nanoparticles could serve as functional materials for efficiently separating small oil droplets from water through the application of a magnetic field. Therefore, P(DMAEMA-b-A-CD)/Fe3O4 nanoparticles held promising potential as materials with economic and commercial value for oil-water separation applications.

Versatile Preparation of Jellyfish-Inspired Color Transition Hydrogels via Polymerization Induced Supramolecular Geletion (PISG)

Supramolecular hydrogels based on host–guest interactions constitute a class of intriguing soft matter and have attracted great attention due to their unique properties, etc. In this study, we successfully synthesized 4-methylene-7-diethylaminocoumarin methacrylate (DEACMMA) monomer and carried out reversible addition-fragmentation chain transfer (RAFT) polymerization using methylated β-cyclodextrin via a host-guest encapsulation mechanism. This process led to the formation of ternary copolymer hydrogel supramolecular photoresponsive hydrogels through polymerization induced supramolecular gelation (PISG). The encapsulation of coumarin monomers by methylated cyclodextrins was confirmed using 2D ROESY NMR and fluorescence spectroscopy. We have carefully analyzed the microstructure of these supramolecular hydrogels by rheological profiles and scanning electron microscopy (SEM). Stimulated by UV light, the copolymers transition from non-luminescence to a bright fluorescent blue color, which is reminiscent of the self-transforming colors observed in jellyfish. The development of photostimuli-responsive hydrogels based on methylated β-cyclodextrin-coated coumarin esters opens new avenues in the fields of smart materials and clinical medicine.

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.

Impact of Zwitterions on the Acidity Constant and Glucose Sensitivity of Block Copolymers with Phenylboronic Acid.

Molecular assemblies that transform in response to pH and saccharide concentration are promising nanomaterials in the field of biomedicine, and polymeric micelles of amphiphilic polymers with phenylboronic acids (PBAs) have been studied. Herein, we report the impact of zwitterions on the acidity constant for the collapse and the glucose sensitivity of a polymeric micelle produced from a diblock copolymer comprising polyacrylamides with PBA and zwitterionic carboxybetaine (PAEBB-b-PCBAAm). The diblock copolymer was synthesized through reversible addition-fragmentation chain-transfer polymerization followed by deprotection. PAEBB-b-PCBAAm produced micellar aggregates in aqueous solutions at a neutral pH, and the polymeric micelles collapsed at a pH of 11.0 because the PBA transformed into a hydroxyboronate anion. The pKa decreased in the presence of glucose owing to boronate ester formation. The PCBAAm chain significantly increased the pH at which the molecular assemblies dissociated. This is probably because the pKa of boronic acid increased through the dipolar interaction of zwitterions, and/or the zwitterionic polymer corona is valid for screening of PBA ionization and electrostatic repulsion of boronate anions. This study on the modulation of pKa through the zwitterionic interaction can facilitate the molecular design of pH- and saccharide-responsive biomaterials.

Star poly(ionic liquid)s: Chain architecture‐property relationships

AbstractIn this study, we report the synthesis of 3‐, 4‐, and 6‐arm star poly(ionic liquid)s (PILs) (specifically, star poly(vinylbenzyl methylimidazolium bis(trifluoromethane)sulfonimide) (poly(VBMIm‐TFSI))) via reversible addition‐fragmentation chain transfer (RAFT) polymerization with a core‐first approach, followed by quaternization and anion exchange. The impact of star polymer architecture on properties was explored by measuring the thermal, mechanical, and ion transport properties of each star PIL compared to those of an analogous linear PIL. The star PILs exhibited up to 2‐fold higher ionic conductivity, 150% higher elastic modulus, and 465% higher ultimate tensile strength compared to the analogous linear PIL. The Williams‐Landel‐Ferry (WLF) equation was employed to explore the effect of increased free volume on the improved ion transport properties of the star PILs. These results highlight the impact of star polymer architecture on PILs and star PILs as promising materials for electrochemical energy devices.

RAFT mediated dispersion copolymerization of glycidyl methacrylate and octadecyl methacrylate

Micrometer sized copolymeric particles of glycidyl methacrylate and octadecyl methacrylate (poly(GMA-co-OMA) were prepared by reversible addition fragmentation chain transfer (RAFT) mediated dispersion copolymerization technique using polyvinyl pyrrolidone (PVP) as steric stabilizer and 2-cyano-2-propyl benzodithioate (CPB) as RAFT agent in ethanol. Different reaction parameters on the characteristics of poly(GMA-co-OMA) particles and their effects were investigated thoroughly in the presence of RAFT agent. Formation of poly(GMA-co-OMA) particle sizes, its stability and morphology depends on the concentration of RAFT agent, stabilizer as well as the monomer ratio. Spherical poly(GMA-co-OMA) particles of size ranges1-13 μm were obtained after optimization of the ratio between GMA and OMA. In the presence of RAFT, with the increased amount of hydrophobic monomer OMA, instabilities of the particles are observed while particle sizes found to be decreased with the increased amount of GMA in the reaction mixture. Prepared poly(GMA-co-OMA) particles were characterized by different analytical techniques such as NMR, IR, GPC, TGA etc. while Field Emission Scanning Electron Microscope (FE-SEM) was applied to study the poly(GMA-co-OMA) particle sizes and its morphology.

UCST-Type Thermoresponsive Sol–Gel Transition Triblock Copolymer Containing Zwitterionic Polymer Blocks

Thermoresponsive sol–gel transition polymers are of significant interest because of their fascinating biomedical applications, including as drug reservoirs for drug delivery systems and scaffolds for tissue engineering. Although extensive research has been conducted on lower critical solution temperature (LCST)-type sol–gel transition polymers, there have been few reports on upper critical solution temperature (UCST)-type sol–gel transition polymers. In this study, we designed an ABA-type triblock copolymer composed of a poly(ethylene glycol) (PEG) block and zwitterionic polymer blocks that exhibit UCST-type thermoresponsive phase transitions. A sulfobetaine (SB) monomer with both ammonium and sulfonate (–SO3) groups in its side chain or a sulfabetaine (SaB) monomer with both ammonium and sulfate (–OSO3) groups in its side chain was polymerized from both ends of the PEG block via reversible addition–fragmentation chain-transfer (RAFT) polymerization to obtain PSB-PEG-PSB and PSaB-PEG-PSaB triblock copolymers, respectively. Although an aqueous solution containing the PSB-PEG-PSB triblock copolymer showed an increase in viscosity upon cooling, it did not undergo a sol-to-gel transition. In contrast, a sol-to-gel transition was observed when a phosphate-buffered saline containing PSaB-PEG-PSaB was cooled from 80 °C to 25 °C. The PSaB blocks with –OSO3 groups exhibited a stronger dipole–dipole interaction than conventional SB with –SO3 groups, leading to intermolecular association and the formation of a gel network composed of PSaB assemblies bridged with PEG. The fascinating UCST-type thermoresponsive sol–gel transition properties of the PSaB-PEG-PSaB triblock copolymer suggest that it can provide a useful platform for designing smart biomaterials, such as drug delivery reservoirs and cell culture scaffolds.

Using RAFT Polymerization Methodologies to Create Branched and Nanogel-Type Copolymers.

This review aims to highlight the most recent advances in the field of the synthesis of branched copolymers and nanogels using reversible addition-fragmentation chain transfer (RAFT) polymerization. RAFT polymerization is a reversible deactivation radical polymerization technique (RDRP) that has gained tremendous attention due to its versatility, compatibility with a plethora of functional monomers, and mild polymerization conditions. These parameters lead to final polymers with good control over the molar mass and narrow molar mass distributions. Branched polymers can be defined as the incorporation of secondary polymer chains to a primary backbone, resulting in a wide range of complex macromolecular architectures, like star-shaped, graft, and hyperbranched polymers and nanogels. These subcategories will be discussed in detail in this review in terms of synthesis routes and properties, mainly in solutions.

Network Polymer Properties Engineered Through Polymer Backbone Dispersity and Structure

AbstractDispersity (Ð or Mw/Mn) is an important parameter in material design and as such can significantly impact the properties of polymers. Here, polymer networks with independent control over the molecular weight and dispersity of the linear chains that form the material are developed. Using a RAFT polymerization approach, a library of polymers with dispersity ranging from 1.2—1.9 for backbone chain‐length (DP) 100, and 1.4—3.1 for backbone chain‐length 200 were developed and transformed to networks through post‐polymerization crosslinking to form disulfide linkers. The tensile, swelling, and adhesive properties were explored, finding that both at DP 100 and DP 200 the swelling ratio, tensile strength, and extensibility were superior at intermediate dispersity (1.3—1.5 for DP 100 and 1.6—2.1 for DP 200) compared to materials with either substantially higher or lower dispersity. Furthermore, adhesive properties for materials with chains of intermediate dispersity at DP 200 revealed enhanced performance compared to the very low or high dispersity chains.

Network Polymer Properties Engineered Through Polymer Backbone Dispersity and Structure.

Dispersity (Ð or Mw/Mn) is an important parameter in material design and as such can significantly impact the properties of polymers. Here, polymer networks with independent control over the molecular weight and dispersity of the linear chains that form the material are developed. Using a RAFT polymerization approach, a library of polymers with dispersity ranging from 1.2-1.9 for backbone chain-length (DP) 100, and 1.4-3.1 for backbone chain-length 200 were developed and transformed to networks through post-polymerization crosslinking to form disulfide linkers. The tensile, swelling, and adhesive properties were explored, finding that both at DP 100 and DP 200 the swelling ratio, tensile strength, and extensibility were superior at intermediate dispersity (1.3-1.5 for DP 100 and 1.6-2.1 for DP 200) compared to materials with either substantially higher or lower dispersity. Furthermore, adhesive properties for materials with chains of intermediate dispersity at DP 200 revealed enhanced performance compared to the very low or high dispersity chains.