Copolymer Materials Research Articles

Synthesis and electrochemical investigation of beta-substituted thiophene-based donor–acceptor copolymers with 3,4-ethylenedioxythiophene (EDOT)

The present work reports the synthesis of four electron-acceptor beta-substituted thiophenes that were studied as monomers for electrochemical polymerization with 3,4-ethylenedioxythiophene (EDOT), an electron-donating monomer, aiming the combination of electron-acceptor and donor monomer thiophene to a simpler and convenient build up of novel donor–acceptor copolymeric materials via electrochemical polymerization. Four novel copolymers poly(EDOT-co-3-thiophene phenylacetate), (PEDOT-co-PPhTAc-2a), poly(EDOT-co-3-thiophene(4-nitrophenyl)acetate) (PEDOT-co-PPhTAc-2b), poly(EDOT-co-3-thiophenephenylcarboxylate) (PEDOT-co-PPhTCb), and poly(EDOT-co-3-(phenoxymethyl)thiophene) (PEDOT-co-PPhOMT) were electrochemically polymerized. The monomers were characterized by spectrometric techniques (FTIR, 1H NMR, and 13C NMR), and the copolymers were identified by electrochemical analyses and FT-IR. Although the corresponding homopolymers could not be obtained, in the presence of EDOT, the copolymers were formed in a quasi-reversible electrochemical kinetics. The infrared spectra of the copolymers as well the electrochemical profile corroborates their obtaining. The mass variation during the electrosynthesis was analyzed using a quartz crystal microbalance. The film’s morphologies were investigated by SEM. Interestingly, the combination of electron-rich monomer thiophene (EDOT) and these electron-deficient carboxy-substituted thiophenes might be a convenient building block couple to increase the performance control of physic-chemical properties of mixed polythiophenes with innovative applications and they also showed a possible applicability as charge storage device.

Multiblock Copolymer Grafting for Butanol Biofuel Recovery by a Sustainable Membrane Process.

Biobutanol is an attractive renewable biofuel mainly obtained by the acetone-butanol-ethanol (ABE) fermentation process. Nevertheless, the alcohol concentration has to be limited to a maximum of 2 wt % in ABE fermentation broths to avoid butanol toxicity to the microorganisms. The pervaporation (PV) membrane process is a key sustainable technology for butanol recovery in these challenging conditions. In this work, the grafting of azido-polydimethylsiloxane (PDMS-N3) onto a PDMS-based multiblock copolymer containing alkyne side groups led to a series of original membrane materials with increasing PDMS contents from 50 to 71 wt %. Their membrane properties were assessed for butanol recovery by pervaporation from a model aqueous solution containing 2 wt % of n-butanol at 50 °C. The membrane flux J50μm for a reference thickness of 50 μm strongly increased from 84 to 192 g/h m(2) with increasing PDMS content for free-standing dense membranes with thicknesses in the range of 38-95 μm. At the same time, the intrinsic butanol permeability increased from 1.47 to 4.68 kg μm/h m(2) kPa and the permeate butanol content was also strongly improved from 38 to 53 wt %, corresponding to high and very high membrane separation factors of 30 and 55, respectively. Therefore, the new grafted copolymer materials strongly overcame the common permeability/selectivity trade-off for butanol recovery by a sustainable membrane process.

Organic vapor sensing properties of copolymer Langmuir-Blodgett thin film sensors

ABSTRACTIn this study, a novel poly[Styrene (ST)-co-Glycidyl Methacrylate (GMA)] copolymer material is used to fabricate Langmuir-Blodgett (LB) thin films and investigate organic vapor sensing properties. Quartz Crystal Microbalance (QCM) system is used to investigate gas sensing performance of copolymer LB films during exposure to Volatile Organic Compounds (VOCs). The poly[Styrene (ST)-co-Glycidyl Methacrylate (GMA)] LB thin film sensor sensitivities are determined to be between 0.12 and 0.25 Hz ppm−1. Detection limits of the copolymer LB thin film are found to be between 23 and 49 ppm against organic vapors. The copolymer LB thin films are more sensitive to chloroform than other vapors used in this study. The results demonstrated that the poly[Styrene (ST)-co-Glycidyl Methacrylate (GMA)] copolymer material is promising as a organic vapor sensing device at room temperature.

Domain morphology, boundaries, and topological defects in biophotonic gyroid nanostructures of butterfly wing scales.

Many organisms in nature have evolved sophisticated cellular mechanisms to produce photonic nanostructures and, in recent years, diverse crystalline symmetries have been identified and related to macroscopic optical properties. However, because we know little about the distributions of domain sizes, the orientations of photonic crystals, and the nature of defects in these structures, we are unable to make the connection between the nanostructure and its development and functionality. We report on nondestructive studies of the morphology of chitinous photonic crystals in butterfly wing scales. Using spatially and angularly resolved x-ray diffraction, we find that the domains are highly oriented with respect to the whole scale, indicating growth from scale boundaries. X-ray coherent diffractive imaging reveals two types of crystalline domain interfaces: abrupt changes between domains emerging from distinct nucleation sites and smooth transitions with edge dislocations presumably resulting from internal stresses during nanostructure development. Our study of the scale structure reveals new aspects of photonic crystal growth in butterfly wings and shows their similarity to block copolymer materials. It opens new avenues to exploration of fundamental processes underlying the growth of biological photonic nanostructures in a variety of species.

Electrospun elastic acrylonitrile butadiene copolymer fibers

Abstract Nitrile rubber (NBR) is an unsaturated copolymer of acrylonitrile and butadiene. Due to its excellent oil-resistance, NBR products are widely used such as in the automotive and aerospace industries. This paper discusses the fabrication of acrylonitrile butadiene copolymer fibers via electrospinning. A transition from electrospray to electrospinning mechanism was observed and investigated by varying the solution composition. Diameter distributions and average diameters of the electrospun fibers from solutions of various copolymer weight concentrations were determined and compared. Water contact angles of both raw material and electrospun fiber mats were measured. Results indicated that the copolymer material was intrinsically hydrophobic, and the electrospun fiber mats showed higher hydrophobicity due to increased surface roughness. These properties were found to be strongly dependent upon the solution concentration. As the solution concentration increased, average fiber diameter increased and water contact angle decreased. Fiber mats of three different basis weights prepared from solutions of 5% copolymer concentration were prepared. Some of the mats were rolled into yarns. The flat mats and yarns were tested for uniaxial tensile strength to obtain data on their stress-strain performance. Comparison the stress-stain data for the flat mats and yarns showed similar properties. Evaluations of the performances of the fiber mats and yarns accounted for the fiber mat basis weights (mass of fibers per area of mat) and mat porosities through application of an idealized parallel fiber mat model. For small strains the stress-strain curves followed similar paths, but at large strains the paths deviated as fiber-fiber bonds slipped or fibers ruptured. For different basis weights, maximum tensile strengths of the flat mats and yarns were close, but slightly varied due to the more complex fiber structures compared to the idealized model. The yarns held larger stresses before rupture and possessed higher maximum tensile strengths than the flat mats attributed to the lower porosity of the yarns and additional bonds between fiber layers that are absent in the flat mats.

Hydroxyl-Exchanged Nanoporous Ionic Copolymer toward Low-Temperature Cycloaddition of Atmospheric Carbon Dioxide into Carbonates.

An ionic copolymer catalyst with nanopores, large surface area, high ionic density, and superior basicity was prepared via the radical copolymerization of amino-functionalized ionic liquid bromide and divinylbenzene, followed with a hydroxyl exchange for removing bromonium. Evaluated in chemical fixation of CO2 with epoxides into cyclic carbonates in the absence of any solvent and basic additive, the nanoporous copolymer catalyst showed high and stable activity, superior to various control catalysts including the halogen-containing analogue. Further, high yields were obtained over a wide scope of substrates including aliphatic long carbon-chain alkyl epoxides and internal epoxide, even under atmospheric pressure and less than 100 °C for the majority of the substrates. On the basis of in situ Fourier transform infrared (FT-IR) investigation and density functional theory (DFT) calculation for the reaction intermediates, we proposed a possible reaction mechanism accounting for the superior catalytic activity of the ionic copolymer. The specifically prepared ionic copolymer material of this work features highly stable, noncorrosive, and sustainable catalysis and, thus, may be a new possibility for efficient chemical fixation of CO2 since it is an environmentally friendly, metal-free solid catalyst.

Simple Extrapolation Method To Predict the Electronic Structure of Conjugated Polymers from Calculations on Oligomers

We introduce two simple tight-binding models, which we call fragment frontier orbital extrapolations (FFOE), to extrapolate important electronic properties to the polymer limit using electronic structure calculations on only a few small oligomers. In particular, we demonstrate by comparison to explicit density functional theory calculations that for long oligomers the energies of the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and of the first electronic excited state are accurately described as a function of number of repeat units by a simple effective Hamiltonian parametrized from electronic structure calculations on monomers, dimers and, optionally, tetramers. For the alternating copolymer materials that currently comprise some of the most efficient polymer organic photovoltaic devices one can use these simple but rigorous models to extrapolate computed properties to the polymer limit based on calculations on a small number of low-molecular-weight oligomers.

Synthesis and characterization of novel UV-curable fluorinated polyurethane-acrylate copolymer

A series of UV-curable fluorinated polyurethane-acrylate(PUA) has been developed by incorporating octafluoropentyl alcohol into the segment of UV-curable polyurethane-acrylate to improve the thermal property and surface property of the copolymer material. The structures of the synthesized polymers were characterized by Fourier transform infrared(FTIR) spectrometry. In order to find out the effect of incorporated fluorine on the UV-cured films, the properties of the UV-cured films were tested through contact angle, water absorption, and thermogravimetric analysis (TGA). The fractured-surface morphologies of the UV-cured coatings were investigated by scanning electron microscopy(SEM). With increasing the content of fluorine segments, the contact angle of the UV-cured films increased and the water absorption decreased, suggesting the fluorine segments migrated and formed a fluorine-covered surface to avoid water penetration. The observation of the fractured-surface morphology through SEM test showed that the fluorinated UV-cured films gained rough fractured-surface compared with the pure UV-cured polyacrylate film, demonstrating the migrating of the fluorine segments. The TGA curves show that the fluorinated UV-cured films gained higher thermal degradation temperature than the virgin UV-cured polyacrylate film. And as increasing the fluorine content, the thermal degradation temperature increased. These phenomena could be reasonably explained by the enrichment of fluorinecontained segment on the surface of the film and the high thermal property due to fluorine atom.

Synthesis and optical properties of white phosphorescent carbazole - iridium copolymers

ABSTRACTA series of novel carbazole-iridium copolymers have been designed and synthesized by the combination of blue-emitting acrylate carbazole M1 with hole transporting property and yellow-emitting cyclometalated iridium complex M2 containing 2-phenylpyridine as main ligand and acrylic acid as auxiliary ligand. The results showed that the blue carbazole host resulted in an efficient energy transfer to the yellow iridium complex guest, and when the feed molar ratio of M1 to M2 was 99:1, the emission spectrum of the copolymer presented a broad peak emission which can cover the whole visible range from 400 to 700 nm to obtain a nearly white copolymer material with the CIE coordinates of (0.30, 0.31), as a consequence of polymerized units luminescence, host-guest energy transfer and conjugation degree. Nevertheless, the host-guest energy transfer resulted in green emission about 524 nm of copolymer as the proportion of iridium complex monomer increased. The fluorescence quantum yields of the copolymers were significantly improved compared to the iridium complex monomer.

Towards a novel positive tone resist mr-PosEBR for high resolution electron-beam lithography

Herein, we present the results of a systematic material development study we carried out in order to obtain a new positive tone resist for high resolution electron-beam lithography. Several acrylic copolymer materials with different mass fractions of the comonomers, different molecular weights and similar molecular weight distributions were synthesized and – as resist solutions – evaluated in terms of electron-beam lithography performance. On the one hand, within the ranges investigated, it was shown that the lithographic sensitivity is significantly influenced by the composition rather than by the molecular weight or molecular weight distribution. On the other hand, the etch resistance of the materials remains unaffected by changes of these parameters. The resist material exhibiting the best combination of the desired properties, mr-PosEBR, is 2 times more sensitive than PMMA (495kDa) and performs comparably to the known high resolution resist ZEP520A. For example, a grating pattern with 29nm wide lines with a period of 100nm could be generated in films of mr-PosEBR with an area dose of 100μC/cm2. In terms of resolution, single lines of only 35nm width could be fabricated via metal lift-off using 100kV EBL. Furthermore, the dry etch stability of mr-PosEBR in a reactive-ion etching (RIE) process (etch gases: CF4/SF6) is similar to the one of ZEP520A (etch rates, mr-PosEBR: 190nm/min, ZEP520A: 150nm/min, silicon: 440nm/min). Moreover, high resolution nanopatterns in mr-PosEBR could be smoothly transferred into the underlying Si substrate by a RIE process.

Surface morphological modification of crosslinked hydrophilic co-polymers by nanosecond pulsed laser irradiation

This work reports an investigation of the surface modifications induced by irradiation with nanosecond laser pulses of ultraviolet and visible wavelengths on crosslinked hydrophilic co-polymeric materials, which have been functionalized with 1-vinylimidazole as a co-monomer. A comparison is made between hydrogels differing in the base co-monomer (N,N-dimethylaminoethyl methacrylate and N-[3-(dimethylamino)propyl] methacrylamide) and in hydration state (both swollen and dried states). Formation of craters is the dominant morphological change observed by ablation in the visible at 532nm, whereas additional, less aggressive surface modifications, chiefly microfoams and roughness, are developed in the ultraviolet at 266nm. At both irradiation wavelengths, threshold values of the incident laser fluence for the observation of the various surface modifications are determined under single-pulse laser irradiation conditions. It is shown that multiple-pulse irradiation at 266nm with a limited number of laser shots can be used alternatively for generating a regular microfoam layer at the surface of dried hydrogels based on N,N-dimethylaminoethyl methacrylate. The observations are rationalized on the basis of currently accepted mechanisms for laser-induced polymer surface modification, with a significant contribution of the laser foaming mechanism. Prospective applications of the laser-foamed hydrogel matrices in biomolecule immobilization are suggested.

Controlled Organocatalytic Ring-Opening Polymerization of ε-Thionocaprolactone.

For the first time, the controlled ring-opening polymerization (ROP) of ε-thionocaprolactone (tnCL) is conducted. The organocatalytic ROP of tnCL occurs without carbonyl scrambling, leading to homopoly(ε-thionocaprolactone) (PtnCL). The ROP by base catalysts alone is proposed to proceed via a nucleophilic mechanism, while the addition of an H-bond donating thiourea (TU) is shown to provide excellent reaction control. The increased reaction control provided by the TU occurs in the virtual absence of binding between tnCL and TU, and a mechanistic account for this observation is discussed. The monomer ring strain is measured and found to be similar to δ-valerolactone (VL). Copolymers with VL are synthesized, and the resulting analysis of the copolymer materials properties provides the only known physical characterizations of poly(thio(no)ester-co-ester)s.

Zwitterionic fibrous polypropylene assembled with amphiphatic carboxybetaine copolymers for hemocompatible blood filtration

The present study serves three main functions. First, it presents a novel random copolymer, made of octadecyl acrylate hydrophobic blocks and 2-(dimethylamino)ethyl methacrylate hydrophilic groups, and it zwitterionic form. Second, random copolymer and zwitterionic random copolymer, OmDn and Z-OmDn, are used to modify polypropylene membranes by evaporation coating. Our investigations unveil that this method leads to sufficiently stable self-assembling provided a minimum number of hydrophobic repeat units of 77, which also corresponds to a hydrophobic degree of 74%. Third, antifouling and hemocompatible properties of membranes are thoroughly investigated using all types of blood cells separately, as well as challenging membranes against whole blood in static and dynamic conditions. Membranes modified with zwitterionic copolymer containing 26% of zwitterionic groups are shown to be highly antifouling and hemocompatible, for a coating density as low as 0.2mg/cm2. Their application in a specially designed blood filtration module enabled to almost totally inhibit blood cells interactions with membrane material, as well as to importantly reduce platelet activation in the permeate (2.5-fold reduction). Statement of SignificanceThe design of new zwitterionic copolymer material is proposed and demonstrated in this study. It was showed that hydrophobicoctadecyl acrylate segments can be introduced in the zwitterioniccarboxybetaine polymer chain with a well-controlled random sequence. Stable, efficient, and effective surface zwitterionization of hydrophobic polypropylene are obtained via grafting onto approach by evaporation-induced self-assembling coating. In the perspective of potential application, hemocompatible blood filtration was demonstrated with the excellent results of non-activated platelets obtained. Summary of ImpactsDesign: New zwitterionicmaterial, amphiphatic carboxybetaine copolymers.Development: Evaporation-induced self-assembling grafting.Application: Hemocompatible blood filtration.

RAFT copolymerization of a phosphorus-containing monomer with α-hydroxy phosphonate and methyl methacrylate

RAFT copolymerization of a phosphorus-containing monomer with α-hydroxy phosphonate PHMA and MMA was successfully conducted and the resultant well-defined copolymer material shows good superior flame-retardant properties and hydrophilicity.

Tailoring copper (II) methacrylate‐containing copolymers and its use as electrode modifier agent in electroanalytical applications

ABSTRACTThis work focuses on the synthesis of a new class of copolymer materials consisting of traditional vinyl monomers (essentially, vinyl acetate, ethyl acrylate, and methyl methacrylate) and copper (II) methacrylate (Cu(II)MA) intended to be used as surface modification agents in electrochemical quantifications of organic and inorganic analytes. Voltammetry assays showed that when deposited on glassy‐carbon electrode (GCE), Cu(II)MA‐based copolymers are very promising materials to be applied in electrochemical determinations, exhibiting high analytical signal in the oxidation and reduction peaks during quantification of potassium hexacyanoferrate (III) in comparison to a bare GCE, contributing to increase the effective electrode area. When employed for the determination of ascorbic acid, PVAcCu(II)MA/GCE exhibited performance similar to that of the bare GCE. Polymers characterizations showed that glass transition temperature of the Cu(II)MA‐based materials increased in approximately 10–20°C, as consequence of the copper present in molecular structure of the copolymer chains (bidentate bridging coordination mode). Energy‐dispersive X‐ray spectroscopy measurements of Cu(II)MA monomer and Cu(II)MA‐based copolymers showed strong characteristic peaks Kα and Kβ at 8.04 and 8.90 keV, respectively, with an average amount of copper of 99%. The performance of the Cu(II)MA‐based copolymers modified electrodes is strongly dependent on the amount of copper into the copolymer chains and consequently on the monomers conversion. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43202.

Study of accessible free volume and transport properties of TFPS-co-TMSP copolymer

Copolymers of 1-trimethylsilyl-1-propyne (TMSP) with 1-(3,3,3-trifluoropropyldimethylsilyl)1-propyne (TFPS) as part of a systematic series with the TFPS content of the final polymer in the range of 0 to 46 mol % have been synthesized. The resulting samples have been characterized by different instrumental methods including NMR, IR, and DSC techniques. It has been shown that the accessible free volume of the polymer decreases from 30.4 to 19.1% with an increase in the proportion of TFPS units. Moreover, the gas transport properties of the membrane materials are reduced by factors of 30 (oxygen), 50 (nitrogen), and 15 (carbon dioxide), although the selectivity for the O2/N2 and CO2/N2 gas pairs increases from 1.6 to 2.5 and 2.5 to 11.5, respectively. A study of nanofiltration of organic media has shown that the ethanol permeability through the TFPS-co-TMSP copolymer material is reduced by no more than 30%, a value that is comparable with the relative decrease in the fractional free volume of the polymer. An increase in the TFPS content has improved the stability of the membrane material in ethanol (swelling ratio decreased from 61 to 39%), thereby resulting in an increase in the retention of the Orange II anionic dye (350 g/mol) from 89 to 94%.

Real-time monitoring of the penetration of amphiphilic acrylate copolymer in leather using a fluorescent copolymer as tracer.

A fluorescent tracer, poly (acrylic-co-stearyl acrylate-co-3-acryloyl fluorescein) [poly (AA-co-SA-co-Ac-Flu)], used for real-time monitoring the penetration of amphiphilic acrylate copolymer, poly (acrylic-co-stearyl acrylate) [poly (AA-co-SA)], in leather was synthesized by radical polymerization of acrylic, stearyl acrylate and fluorescent monomer, 3-acryloyl fluorescein (Ac-Flu). The structure, molecular weight, introduced fluorescent group content and fluorescent characteristics of the fluorescent tracer and target copolymer, amphiphilic acrylate copolymer, were also characterized. The results show that the tracer presents the similar structural characteristics to the target and enough fluorescence intensity with 1.68 wt % of the fluorescent monomer introduced amount. The vertical section of the leather treated with the target copolymer mixing with 7% of the tracer exhibits evident fluorescence, and the change of fluorescence intensity along with the vertical section with treating time increasing can reflect the penetration depth of the target copolymer. The introduction of the fluorescent group in polymer structure through copolymerization with a limited amount of fluorescent monomer, Ac-Flu, is an effective way to make a tracer to monitor the penetration of the target in leather, which provides a new thought for the penetration research of syntans such as vinyl copolymer materials in leather manufacture.

Challenges and Opportunities in the Development of Conjugated Block Copolymers for Photovoltaics

Fully conjugated block copolymers that covalently link donor and acceptor units within the molecular structure have the potential to simultaneously control the mesoscale assembly and interfacial structure. As a consequence, utilizing block copolymers as the active layer provides a unique opportunity to tune charge and energy transfer processes while retaining a mesoscale scaffold for efficient charge extraction within photovoltaic devices. Recent progress in synthesis, structural characterization, modeling, and device fabrication suggest significant advances in block copolymer materials are in the near future—both as model materials for systematic studies of charge and energy transfer and as high performance materials for photovoltaic devices. In this Perspective, we describe recent efforts, current challenges, and opportunities in the development of fully conjugated block copolymers for organic photovoltaics.

Kinetics of directed self-assembly of block copolymers on chemically patterned substrates

Chemically patterned surfaces have been successfully employed to direct the kinetics of self-assembly of block copolymers into dense, periodic morphologies (”chemoepitaxy”). Significant efforts have been directed towards understanding the kinetics of structure formation and, particularly, the formation and annihilation of defects. In the present manuscript we use computer simulations of a soft, coarse-grained polymer model to study the kinetics of structure formation of lamellar-forming block copolymer thin films on a chemical pattern of lines and spaces. The case where the copolymer material replicates the surface pattern and the more subtle scenario of sparse guiding patterns are considered. Our simulation results highlight (1) the importance of the early stages of pattern-directed self-assembly that template the subsequent morphology and (2) the dependence of the free-energy landscape on the incompatibility between the two blocks of the copolymer.

Preparation of Chemically-Tailored Copolymer Membranes with Tunable Ion Transport Properties.

Membranes derived from copolymer materials are a promising platform due to their straightforward fabrication and small yet tunable pore structures. However, most current applications of these membranes are limited to the size-selective filtration of solutes. In this study, to advance the utility of copolymer membranes beyond size-selective filtrations, a poly(acrylonitrile-r-oligo(ethylene glycol) methyl ether methacrylate-r-glycidyl methacrylate) (P(AN-r-OEGMA-r-GMA)) copolymer is used to fabricate membranes that can be chemically modified via straightforward schemes. The P(AN-r-OEGMA-r-GMA) copolymer is cast into asymmetric membranes using a nonsolvent induced phase separation technique. Then, the surface charge of the membrane is modified to tailor its performance for nanofiltration applications. The oxirane groups of the glycidyl methacrylate (GMA) moiety that line the pore walls of the membrane allows for both positively charged and negatively charged moieties to be introduced directly without any prior activation. Notably, the highly size-selective nanostructure of the copolymer materials is retained throughout the functionalization processes. Specifically, amine moieties are attached to the pore walls using the aminolysis of the oxirane groups. The resulting amine-functionalized membrane is positively charged and rejects up to 87% of the salt dissolved in a 10 mM magnesium chloride feed solution. Further modification of the amine-functionalized membrane with 4-sulfophenyl isothiocyanate results in pore walls lined by sulfonic acid moieties. These negatively charged membranes reject up to 90% of a 10 mM sodium sulfate feed solution. Throughout the modification scheme, the membrane permeability remains equal to 1.5 L m(-2) h(-1) bar(-1) and the rejection of neutral solutes (i.e., sucrose and poly(ethylene oxide)) is consistent with the membrane having a single well-defined pore diameter of ∼5 nm. The performance of the membrane as a function of ion valence number, solution pH, and ionic strength is investigated.