Comonomer Ratio Research Articles

Recyclable cellulose-based vitrimer electrolytes for lithium ion batteries

Cellulose as polymer electrolytes in lithium-ion batteries (LIBs) has a number of advantages such as low cost, readily available, abundant, environmentally friendly, and contains electron-donating groups within its structure. Beside, vitrimers are a novel class of polymer materials made of dynamic covalent networks that can undergo bond-exchange processes. Beyond cellulose's special qualities, cellulose-based vitrimer production is highly desired for enhancing electrolytes mechanical qualities, thermal stability, cyclability, and ionic conductivity. In this study, cellulose-based vitrimeric polymer electrolytes are prepared. At first, poly(glycidyl methacrylate-co-methyl acrylate) by different ratios of comonomers is prepared and then cellulose is cross-linked by prepared copolymers. Prepared vitrimers are recycled four steps through transesterification reaction and as-prepared and recycled crosslinked celluloses are used as gel polymer electrolytes (GPEs). The results showed the best ionic conductivity of as-prepared samples in order of 10−4 S/cm whereas ionic conductivity increased to order of 10−3 S/cm for recycled samples. Also, high lithium-ion transfer number of >0.8 was achieved for recycled samples. All as-prepared and recycled electrolytes had excellent electrochemical stability window (> 5 V). Also, improved specific capacity (>178 mA h g−1 with capacity retention upper than 90 % after 200 cycles at 0.2C of LiCoO2/GPEs/Gr) was attained.

The Influence of the Comonomer Ratio and Reaction Temperature on the Mechanical, Thermal, and Morphological Properties of Lignin Oil-Sulfur Composites.

Although lignin is a plentiful biomass resource, it continually exists as an underutilized component of biomass material. Elemental sulfur is another abundant yet underutilized commodity produced as a by-product resulting from the refining of fossil fuels. The current study presents a strategy for preparing five durable composites via a simple one-pot synthesis involving the reaction of lignin oil and elemental sulfur. These lignin oil-sulfur composites LOSx@T (where x = wt. % sulfur, ranging from 80 to 90, and T represents the reaction temperature in °C) were prepared via the reaction of elemental sulfur and lignin oil (LO) with elemental sulfur. The resulting composites could be remelted and reshaped several times without the loss of mechanical strength. Mechanical, thermal, and morphological studies showed that LOSx@T possesses properties competitive with some mechanical properties of commercial building materials, exhibiting favorable compressive strengths (22.1-35.9 MPa) and flexural strengths (5.7-6.5 MPa) exceeding the values required for many construction applications of ordinary Portland cement (OPC) and brick formulations. While varying the amount of organic material did not result in a notable difference in mechanical strength, increasing the reaction temperature from 230 to 300 °C resulted in a significant increase in compressive strength. The results reported herein reveal potential applications of both lignin and waste sulfur during the ongoing effort toward developing recyclable and sustainable building materials.

Synthesis of ZnO/Poly(Styrene‐co‐Methacrylic Acid) Hybrid Polymer Particles for Enhanced UV‐Visible Photodegradation of Methylene Blue

AbstractIn this study, a series of submicron‐sized functional polymer particles poly(Sty‐co‐MAA) with variable methacrylic acid (MAA) content were prepared by soap‐free emulsion polymerization of styrene (Sty), methacrylic acid (MAA), and ethylene glycol dimethacrylate (EGDMA). The number‐average diameters of polymer particles (Dn) were in the range of 0.11 to 0.19 μm. A decrease in particle size was observed with increasing the molar ratio of MAA comonomer in the recipe. ZnO/poly(Sty‐co‐MAA) hybrid polymer particles were prepared by seeded emulsion copolymerization in presence of zinc oxide nanoparticles (ZnO NPs) as seed particles synthesized using Citrus lemon aqueous leaf extract. Scanning electron microscopy (SEM), transmission electron microsphere (TEM), X‐Ray Diffraction (XRD), and Fourier transformed infra‐red (FT‐IR) analysis were performed to characterize polymer particles. The crystalline size of ZnO NPs and ZnO/poly(Sty‐co‐MAA) hybrid polymer particles calculated from XRD analysis were 20.75 and 29.85 nm, respectively. These hybrid polymer particles were applied as photocatalyst in the photodegradation of methylene blue (MB) dye under UV irradiation, which showed high catalytic activity with degradation efficiency of 85.70 % at room temperature compared to bare ZnO NPs.

Controlled Radical Copolymerization toward Tailored F/N Hybrid Polymers by Using Light‐Driven Organocatalysis

AbstractControlled radical copolymerizations present attractive avenues to obtain polymers with complicated compositions and sequences. In this work, we report the development of a visible‐light‐driven organocatalyzed controlled copolymerization of fluoroalkenes and acyclic N‐vinylamides for the first time. The approach enables the on‐demand synthesis of a broad scope of amide‐functionalized main‐chain fluoropolymers via novel fluorinated thiocarbamates, facilitating regulations over chemical compositions and alternating fractions by rationally selecting comonomer pairs and ratios. This method allows temporally controlled chain‐growth by external light, and maintains high chain‐end fidelity that promotes facile preparation of block sequences. Notably, the obtained F/N hybrid polymers, upon hydrolysis, afford free amino‐substituted fluoropolymers versatile for post modifications toward various functionalities (e.g., amide, sulfonamide, carbamide, thiocarbamide). We further demonstrate the in situ formation of polymer networks with desirable properties as protective layers on lithium metal anodes, presenting a promising avenue for advancing lithium metal batteries.

Controlled Radical Copolymerization toward Tailored F/N Hybrid Polymers by Using Light-Driven Organocatalysis.

Controlled radical copolymerizations present attractive avenues to obtain polymers with complicated compositions and sequences. In this work, we report the development of a visible-light-driven organocatalyzed controlled copolymerization of fluoroalkenes and acyclic N-vinylamides for the first time. The approach enables the on-demand synthesis of a broad scope of amide-functionalized main-chain fluoropolymers via novel fluorinated thiocarbamates, facilitating regulations over chemical compositions and alternating fractions by rationally selecting comonomer pairs and ratios. This method allows temporally controlled chain-growth by external light, and maintains high chain-end fidelity that promotes facile preparation of block sequences. Notably, the obtained F/N hybrid polymers, upon hydrolysis, afford free amino-substituted fluoropolymers versatile for post modifications toward various functionalities (e.g., amide, sulfonamide, carbamide, thiocarbamide). We further demonstrate the in situ formation of polymer networks with desirable properties as protective layers on lithium metal anodes, presenting a promising avenue for advancing lithium metal batteries.

Fluorescent Aromatic Polyether Sulfones: Processable, Scalable, Efficient, and Stable Polymer Emitters and Their Single-Layer Polymer Light-Emitting Diodes.

In this study, fully aromatic polyether sulfones were developed, bearing blue, yellow, and orange-red π-conjugated semiconducting units. Carbazole-, anthracene-, and benzothiadiazole-based fluorophores are copolymerized with a diphenylsulfone moiety. A diphenylpyridine comonomer was additionally utilized, acting as both a solubilizing unit and a weak blue fluorescent group. Using this rationale, fluorescent polyarylethers with high molecular weights, up to 70 kDa, were developed, showing film formation ability and high thermal stability, while preserving excellent solubility in common organic, nonvolatile, and nonchlorinated solvents. Fine-tuning of the emission color was achieved through subtle changes of the comonomers' type and ratio. Single-chromophore-bearing copolymers emitted in the blue or the yellow region of the visible spectrum, while the dual-chromophore-bearing terpolymers emitted throughout the visible spectrum, resulting in white light emission. Solutions of 20 wt% in polar aprotic solvents at ambient conditions allowed the deposition of fluorescent copolyethers and printing from non-chlorinated solvents. All polyethers were evaluated for their structural and optoelectronic properties, and selected copolymers were successfully used in the emitting layer (EML) of organic light-emitting diode (OLED) devices, using either rigid or flexible substrates. Remarkable color stability was displayed in all cases for up to 15 V of bias voltage. The Commission Internationale de L'Eclairage (CIE) of the fabricated devices is located in the blue (0.16, 0.16), yellow (0.44, 0.50), or white region of the visible spectrum (0.33, 0.38) with minimal changes according to the ratio of the comonomers. The versatile methodology toward semiconducting polyethersulfones for polymer light-emitting diodes (PLEDs) developed herein led to the scaled-up production of luminescent polymers of up to 25 g of high-molecular-weight single batches, demonstrating the effectiveness of this approach as a straightforward tool to facilitate the synthesis of flexible and printable EMLs for large-area PLED coverage.

Simple strategy of the use of pharmaceutically functionalized ionic liquids in a new generation of polymer nanocarriers for the combined delivery of ionic p-aminosalicylate and ampicillin

Single and dual bioactive linear poly(ionic liquid)s (PIL) were synthesized for use as nanocarriers in drug delivery systems (DDS). These PILs were obtained through the (co)polymerization of the choline-based monomeric ionic liquids (MIL) with pharmaceutical anions possessing antibacterial properties, specifically [2-(methacryloyloxy)ethyl]trimethyl-ammonium with ampicillin and p-aminosalicylate (TMAMA/AMP and TMAMA/PAS). The copolymers exhibited varying chain lengths defined by a degree of polymerization (DPn = 122–370), and differing contents of ionic fraction and drugs (TMAMA 61–92 %, AMP 61–93 % and PAS 16–21 %). These parameters were adjustable by the monomer conversion (33–92 %) and the initial ratio of comonomers. In aqueous solution, the polymer particles reached nanosizes, i.e. 190–328 nm for AMP systems and 200–235 nm for AMP/PAS systems. In the release process, the pharmaceutical anions were released through exchange by phosphate anions in PBS at pH 7.4 at 37 °C. Depending on the copolymer composition the release of AMP was attained in 72–100 % (11.1–19.5 µg/mL) within 26 h by the single drug systems, while the dual drug systems released 61–100 % of AMP (14.8–24.7 µg/mL) and 82–100 % of PAS (3.1–4.8 µg/mL) within 72 h. The effectiveness in the drug delivery of the designed TMAMA polymers seems to be promising for future applications in antibiotic therapy and the combined therapy.

Improvement in dielectric properties of polyacrylate copolymers by engineering the interphase region with polymer-grafted reduced graphene oxide

In this study, an innovative interfacial design strategy aimed to investigate the effects of interfacial interactions between the matrix and reduced graphene oxide (rGO) on the dielectric properties of nanocomposites. The polymer matrices with varying comonomer ratios of butyl acrylate and methyl methacrylate were synthesized to deliberately engineer diverse interfacial interactions with polymer-grafted reduced graphene oxide. Through this approach, fine-tuned interfacial interactions between the polymer matrix and polymer-grafted rGO were achieved, which was verified by FE-SEM, DSC, and DMTA analysis. Subsequently, the dielectric properties of the nanocomposites were investigated to elucidate the relationship between interfacial strength and dielectric efficiency. It was found that polymer nanocomposites with enhanced interfacial interactions exhibit higher dielectric permittivity compared to the neat matrix. This enhancement was attributed to the increased charge storage in the interfacial area and improved alignment of polarizable polymer chains in the interphase between the polymer matrix and polymer-grafted rGO.

Influence of vinyl acetate content on the performance of alkyl fumarate copolymers as crude oil flow improvers

Paraffin deposition during waxy crude oil transportation may obstruct the effective flow and pose serious flow assurance issues. Therefore, copolymers are used as flow improvers (FIs) and pour point depressants (PPDs) during chemical treatment programs. The performance of the copolymers is affected by their structure, particularly by the proportion of polar and non-polar segments. Fumarate copolymers are promising PPDs and FIs for waxy crude oils. However, research on the impact of different molar ratios of polar to non-polar units is limited. In this study, dialkyl fumarate–vinyl acetate copolymers with similar molar weights but different comonomer ratios were synthesized. Rheological tests of Akshabulak crude oil doped with the prepared additives and pour point measurements revealed that the efficiency of the synthesized FIs depended on the vinyl acetate content. The most effective performance was achieved from the copolymer with 58–59% (mol) of vinyl acetate. Thus, the efficiency of crude-oil FIs based on alkyl fumarate copolymers can be improved by changing the monomer ratio.

A Spontaneous In Situ Thiol-Ene Crosslinking Hydrogel with Thermo-Responsive Mechanical Properties.

The thermo-responsive behavior of Poly(N-isopropylacrylamide) makes it an ideal candidate to easily embed cells and allows the polymer mixture to be injected. However, P(NiPAAm) hydrogels possess minor mechanical properties. To increase the mechanical properties, a covalent bond is introduced into the P(NIPAAm) network through a biocompatible thiol-ene click-reaction by mixing two polymer solutions. Co-polymers with variable thiol or acrylate groups to thermo-responsive co-monomer ratios, ranging from 1% to 10%, were synthesized. Precise control of the crosslink density allowed customization of the hydrogel's mechanical properties to match different tissue stiffness levels. Increasing the temperature of the hydrogel above its transition temperature of 31 °C induced the formation of additional physical interactions. These additional interactions both further increased the stiffness of the material and impacted its relaxation behavior. The developed optimized hydrogels reach stiffnesses more than ten times higher compared to the state of the art using similar polymers. Furthermore, when adding cells to the precursor polymer solutions, homogeneous thermo-responsive hydrogels with good cell viability were created upon mixing. In future work, the influence of the mechanical micro-environment on the cell's behavior can be studied in vitro in a continuous manner by changing the incubation temperature.

Synthesis and Properties of Vinyl Ether and Acrylonitrile Copolymers

AbstractThe radical copolymerizations of vinyl ethers, including ethylene glycol monovinyl ether (HEVE) and isobutyl vinyl ether (IBVE), and acrylonitrile (AN) are investigated. The reactivity ratios of comonomers are evaluated by Fineman–Ross (rHEVE = 0.032 and rAN = 1.054, and rIBVE = 0.031 and rAN = 13.984) and Kelen–Tudos (rHEVE = 0.001 and rAN = 1.036, and rIBVE = 0.032 and rAN = 13.981) methods, respectively. The conversions of HEVE and IBVE under similar conditions also support that HEVE has a higher reactivity than that of IBVE. A series of poly(HEVE‐co‐AN)s (Mn from 56 000 to 110 000) and poly(IBVE‐co‐AN)s (Mn from 52 000 to 97 000) with random sequential structure are prepared. Furthermore, the glass transitional temperatures of poly(vinyl ether‐co‐AN)s decrease with the increase of vinyl ether units in the copolymers. Thermal stability of poly(vinyl ether‐co‐AN)s is comparable, which is slightly affected by vinyl ether contents. Poly(HEVE‐co‐AN)s possess a two‐stage weight loss (one around 230 °C, and the other around 300 °C), and poly(IBVE‐co‐AN)s decompose at around 350 °C with one stage. In addition, the poly(HEVE‐co‐AN)s demonstrate a good hydrophilicity of which the average of static water contact angles decrease from 85.4° to 62.4° with the HEVE units increased from 8% to 33%.

Синтез и сополимеризация бензамидметакрилата со стиролом

It has been synthesized a new monomer — benzamide methacrylate and its free radical copolymerization with styrene in mass and solution in benzene in the presence of diazoisobutyric acid AIBN) has been carried out and investigated. The ratio of comonomers was changed in the range of 90:10 – 10:90 mol. %. The total concentration of comonomers is 1.7 mol/l at temperature 70 °C. The composition of the synthesized copolymers was determined by the method of elemental analysis on nitrogen content. The monomer and copolymer have been characterized by spectroscopic methods (IR and NMR). The relative activity constant values of the monomer have been determined and Q – e parameters according to Alfrey – Price have been calculated. For estimation of the nature of the links distribution in the macromolecular chain, the microstructure parameters have been calculated. It has been revealed that in all cases r1 > r2, therefore the copolymer is enriched with benzamide methacrylate links. It has been found that the composition of the formed copolymers depends on the composition of the initial monomer mixture. It has been established that the obtained copolymer has a sufficiently high medical-biological activity, which opens up the possibility of using it as bactericides and fungicides. It has been shown that the copolymers obtained on the basis of benzamide methacrylate are non-toxic and can be used as bactericidal preparations. It has been revealed that the biocidal effect has been primarily connected with the availability of benzamide fragment links in the macro-chain.

Effect of chain architecture and comonomer ratio on the biodegradability and thermal stability of biodegradable copolymers of l-lactide and δ-valerolactone

Novel biodegradable copolymers of ʟ-lactide (LA) and δ-valerolactone (VL) were bulk polymerized using stannous octoate as a catalyst initiated with salicylic acid or benzyl alcohol via ring-expansion or ring-opening polymerization, respectively.

Collagen-decorated electrospun scaffolds of unsaturated copolyesters for bone tissue regeneration.

Many efforts have been devoted to bone tissue to regenerate damaged tissues, and the development of new biocompatible materials that match the biological, mechanical, and chemical features required for this application is crucial. Herein, a collagen-decorated scaffold was prepared via electrospinning using a synthesized unsaturated copolyester (poly(globalide-co-pentadecalactone)), followed by two coupling reactions: thiol-ene functionalization with cysteine and further conjugation via EDC/NHS chemistry with collagen, aiming to design a bone tissue regeneration device with improved hydrophilicity and cell viability. Comonomer ratios were varied, affecting the copolymer's thermal and chemical properties and highlighting the tunable features of this copolyester. Functionalization with cysteine created new carboxyl and amine groups needed for bioconjugation with collagen, which is responsible for providing biological and structural integrity to the extra-cellular matrix. Bioconjugation with collagen turned the scaffold highly hydrophilic, decreasing its contact angle from 107 ± 2° to 0°, decreasing the copolymer crystallinity by 71%, and improving cell viability by 85% compared with the raw scaffold, thus promoting cell growth and proliferation. The highly efficient and biosafe strategy to conjugate polymers and proteins created a promising device for bone repair in tissue engineering.

High free volume polymers of intrinsic microporosity for efficient solar thermal fuels with enhanced energy storage capacity

Anchoring photoswitches on high free volume polymers is an emerging strategy to prepare high-performance solar thermal fuels (STFs), however, it still lacks a deep understanding about the relationship between free volume and energy storage performance. Herein, a bottom-to-up strategy was developed to prepare azobenzene-based STFs based on polymers of intrinsic microporosity (Azo-PIMs), in which free volumes could be changed by controlling the feeding ratio of co-monomers. Azo-PIM-1 and Azo-PIM-2 were prepared to have 7.41% and 19.07% azo grafting densities, respectively. The fractional free volume (FFV) and specific surface areas of Azo-PIM-1 are 0.17 and 552.8 m2 g−1, respectively, which are higher than that of Azo-PIM-2 (0.15 and 335.5 m2 g−1) due to the lower azo grafting density. The energy densities (EDg) of Azo-PIM-1 and Azo-PIM-2 in cis isomers are 13.39 J g−1 and 36.75 J g−1, and the corresponding storage enthalpy (ΔH) are 88.53 kJ mol−1 and 103. 35 kJ mol−1, respectively. Their ΔH are higher than that of the azo monomer of 83.76 kJ mol−1, demonstrating that PIMs as templates can efficiently increase the stored energy per azo moiety. Meanwhile, the higher ΔH of Azo-PIM-2 than that of Azo-PIM-1 indicates that the reduced free volume can enhance the energy storage capacity by prohibiting the rotation of azo photoisomerization. This work provides a basis for understanding the role of free volume on the energy storage performance of polymer-based STFs.

Organosilicon copolymers containing triazole and triethoxysilyl groups as the basis for promising functional hydrophobic materials

New functional heat-resistant poly (1-vinyl-1,2,4-triazole-co-triethoxyvinylsilane) (poly (VT-co-TEVS)) copolymers of various compositions containing triazole and triethoxysilyl groups in the side chains were synthesized by radical copolymerization. Elemental analysis, Fourier transform infrared spectroscopy, NMR spectroscopy, gel permeation chromatography, dynamic light scattering, scanning electron microscopy, thermogravimetric analysis, and differential scanning calorimetry were used to study the composition and structure of poly (VT-co-TEVS) copolymers. The weight average molecular weight of the copolymers varies from 21 to 174 kDa. The reactivity ratios of comonomers in copolymerization (rVT = 4.004 and rTEVS = 0.227) indicate the high reactivity of VT. The resulting copolymers exhibit high thermal stability up to 270 °C. Modification of flexible chain poly (VT-co-TEVS) copolymers was carried out using hydrolytic polycondensation of triethoxysilyl groups. Monitoring of the hydrodynamic diameters of the synthesized copolymers showed intermacromolecular crosslinking of polymer chains due to the formation of Si–O–Si siloxane bonds. Based on spatially cross-linked polyorganosiloxanes containing a functional 1,2,4-triazole fragment, hydrophobic heat-resistant polymeric materials were obtained.

Formulation and process determined fouling prediction for the continuous emulsion co polymerisation of vinyl acetate

Fouling is challenging for the industrial implementation of continuous emulsion polymerisations. A requirement for the development of successful anti-fouling concepts is an in-depth understanding of the processes involved in fouling and the knowledge of the main influencing factors. In this work, an experiment-based strategy was developed for the quantification of fouling trends and in order to calculate the expected fouling intensities during the continuous emulsion polymerisation of vinyl acetate copolymers. These, then, can be correlated with the direct process parameters temperature, initiator and emulsifier content and comonomer ratio. The expected fouling tendency for formulations could be determined in the investigated range with an accuracy of ± 15% referred to experimental validations.

Synthesis and Characterization of Novel Wholly Aromatic Copolyesters Based on 4'-Hydroxybiphenyl-3-Carboxylic and 3-Hydroxybenzoic Acids.

A series of new wholly aromatic (co)polyesters based on m-substituted bifunctional comonomers-4'-hydroxybiphenyl-3-carboxylic (3HBCA) and 3-hydroxybenzoic (3HBA) acids with molar ratios of 3HBCA:3HBA from 0:100 to 60:40, respectively-was synthesized. NMR and FTIR spectroscopy methods proved the full compliance of the copolymer composition with the target ratio of comonomers, as well as high compositional homogeneity (absence of block sequences). The resulting copolyesters have a sufficiently high molecular weight and their intrinsic viscosity values are in the range of 0.6-0.8 dL/g. Thermal analysis showed that all 3HBCA-3HBA copolyesters are amorphous, and with an increase in the content of biphenyl units (3HBCA), the glass transition temperature increases significantly (up to 190 °C). The onset of the intense thermal decomposition of the synthesized polyesters occurs above 450 °C. Thus, this indicates a sufficiently high thermal stability of these polyesters. Rheological measurements have shown that melts of copolyesters with a high content of 3HBCA units exhibit anisotropic properties. At the same time, the method of polarization optical microscopy did not confirm the transition to the liquid crystal state for these polyesters. These results confirm that it is possible to obtain high-performance polyesters based on 3HBCA, but not a mesogenic comonomer. Thus, 3HBCA is a promising comonomer for the synthesis of new thermotropic copolyesters with controlled anisotropic properties.

Synthesis and characterization of positive volume phase transition hydrogel membrane prepared using a cellulose substrate

ABSTRACT Thermo-responsive hydrogels display swell-collapse behavior in response to changing temperature. While the hydrogels themselves have many applications such as environmental and chemical separations, the hydrogel can be incorporated within a membrane substrate to improve its mechanical properties and expand the opportunities for development and implementation. The present work describes synthesis of positive volume transition temperature responsive poly(acrylamide-co-acrylic acid) hydrogels on cellulose paper substrates. Effects of factors including co-monomer ratios, degree of crosslinking and mass loading are assessed for Series A random copolymer hydrogels in terms of permeability response. Examination of the membranes is then extended to investigate inter-penetrating networks (IPN) between acrylamide and acrylic acid homo-polymer hydrogels. Series B membranes explore the impact of nonpolar ligands on temperature response through addition of butyl methacrylate co-monomer. For both random copolymer and IPN hydrogel membranes, mass loading dominates permeability performance, though certain criteria must be met. Performance of the Series A membranes was found to be ideal when monomer ratio was 1:1 and there was a lower degree of crosslinking. Addition of butyl methacrylate did not appear to have a consistent impact on the membrane response, appearing to be tied to the degree of crosslinking for random copolymer hydrogel coatings.

Nitroxide-Containing Amphiphilic Random Terpolymers for Marine Antifouling and Fouling-Release Coatings

Two types of amphiphilic random terpolymers, poly(ethylene glycol methyl ether methacrylate)-ran-poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate)-ran-poly(polydimethyl siloxane methacrylate) (PEGMEMA-r-PTMA-r-PDMSMA), were synthesized and evaluated for antifouling (AF) and fouling-release (FR) properties using diverse marine fouling organisms. In the first stage of production, the two respective precursor amine terpolymers containing (2,2,6,6-tetramethyl-4-piperidyl methacrylate) units (PEGMEMA-r-PTMPM-r-PDMSMA) were synthesized by atom transfer radical polymerization using various comonomer ratios and two initiators: alkyl halide and fluoroalkyl halide. In the second stage, these were selectively oxidized to introduce nitroxide radical functionalities. Finally, the terpolymers were incorporated into a PDMS host matrix to create coatings. AF and FR properties were examined using the alga Ulva linza, the barnacle Balanus improvisus, and the tubeworm Ficopomatus enigmaticus. The effects of comonomer ratios on surface properties and fouling assay results for each set of coatings are discussed in detail. There were marked differences in the effectiveness of these systems against the different fouling organisms. The terpolymers had distinct advantages over monopolymeric systems across the different organisms, and the nonfluorinated PEG and nitroxide combination was identified as the most effective formulation against B. improvisus and F. enigmaticus.