Ester Side Groups Research Articles

Ultra-high cross-linked active ester-cured epoxy resins: Side group cross-linking for performance enhancement

Active ester hardeners are a unique class of epoxy hardeners that undergo a curing reaction without generating secondary hydroxyl groups. This characteristic enables the production of low dielectric and low moisture absorption epoxy resins. In this study, two active ester hardeners, bisphenol A diisobutyrate (DIB) and bisphenol A dimethacrylate (DMA), were used to prepare epoxy resins by reacting with a resveratrol-based epoxy monomer (REP). By cross-linking the double bonds in the resin (using dicumyl peroxide, DCP), the properties of the resin can be dramatically changed. Among the resins prepared, REP/DMA/DCP exhibited the highest cross-linking density, approximately 48 times that of REP/DIB. Its storage modulus at 300 °C remained at 600 MPa, indicating an equivalent glass transition temperature (Tg) higher than 300 °C. Additionally, the cross-linking of the ester side groups increased the initial degradation temperature by 12–13 °C, reaching 395–396 °C. Regarding the coefficient of thermal expansion (CTE), the cross-linking of ester side groups had no significant effect on the CTE in the glassy state. However, it drastically reduced the CTE above the glass transition temperature. The average CTE (30–300 °C) of REP/DMA/DCP was only 106 ppm/°C. Furthermore, the cross-linking of the ester side groups appeared to reduce the dielectric constant but increased the dielectric loss and the water absorption rate. Nevertheless, REP/DMA/DCP's dielectric constant at 10 MHz of 3.07, dielectric loss of 0.01, and saturated water absorption of 0.77 wt% remain in the low range.

Design, Synthesis and Aromaticity of an Alternating Cyclo[4]Thiophene[4]Furan.

A new class of conjugated macrocycle, the cyclo[4]thiophene[4]furan hexyl ester (C4TE4FE), is reported. This cycle consists of alternating α-linked thiophene-3-ester and furan-3-ester repeat units, and was prepared in a single step using Suzuki-Miyaura cross-coupling of a 2-(thiophen-2-yl)furan monomer. The ester side groups help promote a syn conformation of the heterocycles, which enables formation of the macrocycle. Cyclic voltammetry studies revealed that C4TE4FE could undergo multiple oxidations, so treatment with SbCl5 resulted in formation of the [C4TE4FE]2+ dication. Computational work, paired with 1 H NMR spectroscopy of the dication, revealed that the cycle becomes globally aromatic upon 2e- oxidation, as the annulene pathway along the outer ring becomes Hückel aromatic. The change in ring current for the cycle upon oxidation was clear from 1 H NMR spectroscopy, as the protons of the thiophene and furan rings shifted downfield by nearly 6 ppm. This work highlights the potential of sequence control in furan-based macrocycles to tune electronic properties.

Engineering Double Load-Sharing Network in Thermosetting: Much More than Just Toughening

Current synthetic epoxy thermosets exhibit a trade-off between stiffness and toughness. Despite the urgent demands for highly stiff and tough epoxy thermosetting resins, existing technologies have struggled to attain resins that satisfy this balance. To circumvent this inherent trade-off, a new strategy to obtain a double load-sharing epoxy thermoset network via hierarchical curing process without adding any other filler is proposed. In the epoxy resin bearing acetyl ester side groups cured by an aromatic amine, the “in situ” step-growth phase-separated morphologies and hydrogen-bonding interactions between hydroxyl groups and the ester groups, which endow the resin with high strength and toughness, can be easily controlled by simply tuning the feed ratio of the amine curing agent. Notably, previously unachievable control of mechanical properties is attained, the processing performance is improved, and the product resists hydrothermal aging. The successful application of this strategy provides promising perspectives for construction versatile and high-performance thermosetting.

Effect of side-group structure and temperature on chain transfer to polymer and branching in acrylate homopolymerizations

The paper reports studies of the effects of ester side-group size and structure on chain transfer to polymer (CTP) and mol% branches (%br) in the final polymers from monomer-starved semi-batch emulsion homopolymerizations of a series of alkyl acrylates with different numbers of ester OR side-group carbon atoms (NsgC) in the range 1–10. Although the high instantaneous conversions and high gel contents in the final polymers show that intermolecular CTP is significant, the kinetics have been analysed principally in terms of intramolecular CTP (intraCTP) because this is expected to be numerically the dominant CTP process. For linear OR side groups, there is a small, continuous increase in %br (from ~ 3.4 to ~ 5.0 mol%) as NsgC increases from 1 to 8, which arises predominantly from the acrylate molar mass (Macrylate) reducing the molar monomer concentration and from the small increase in rate coefficient for propagation (kp) as NsgC increases; no discernible effects of NsgC on the rate coefficient for intraCTP ({k}_{mathrm{trP}}^{mathrm{intra}}) are evident. For isomeric butyl acrylates, there is no measurable effect of isomer structure on %br (4.3–4.4 mol%), indicating that butyl groups are too small for changes in side-group bulkiness to influence {k}_{mathrm{trP}}^{mathrm{intra}} and kp. A similar observation was made for n-hexyl acrylate (nHA) and 2-ethylbutyl acrylate (%br 4.7–4.8 mol%). However, cyclohexyl acrylate (cHA) gives a much higher %br (~ 7.2 mol%), which has been assigned to steric effects increasing {k}_{mathrm{trP}}^{mathrm{intra}} because kp values for nHA and cHA are very similar. For OR side-groups with NsgC of 8 and10, there is a strong effect of side-group non-linearity (2-ethylhexyl, iso-octyl and iso-decyl) increasing %br, with polymers from n-alkyl acrylates having much lower %br (~ 4.5–5.0 mol%) than those from the equivalent non-linear acrylates (~ 6.7–7.1 mol%); since the kp values are expected to be similar for these acrylates, it is evident that the much bulkier non-linear OR groups cause a significant increase in {k}_{mathrm{trP}}^{mathrm{intra}} compared to the linear equivalents. Tentative hypotheses for these steric effects have been postulated. Studies of the effect of temperature (0–80 °C) on CTP and %br for methyl acrylate solution homopolymerization (in which intraCTP should be completely dominant) show the expected reduction in %br as temperature reduces, such that CTP is negligible at 0 °C; Arrhenius analysis gives an activation energy of 40.7 kJ mol−1 for intraCTP, which is within the range of values reported for n-butyl acrylate.

Influence of different ester side groups in polymers on the vapor phase infiltration with trimethyl aluminum.

The vapor phase infiltration (VPI) process of trimethyl aluminum (TMA) into poly(4-acetoxystyrene) (POAcSt), poly(nonyl methacrylate) (PNMA) and poly(tert-butyl methacrylate) (PtBMA) is reported. Depth-profiling X-ray photoelectron spectroscopy (XPS) measurements are used for the first time for VPI based hybrid materials to determine the aluminum content over the polymer film thickness. An understanding of the reaction mechanism on the interaction of TMA infiltrating into the different polymers was obtained through infrared (IR) spectroscopy supported by density functional theory (DFT) studies. It is shown that the loading with aluminum is highly dependent on the respective ester side group of the used polymer, which is observed to be the reactive site for TMA during the infiltration. IR spectroscopy hints that the infiltration is incomplete for POAcSt and PNMA, as indicated by the characteristic vibration bands of the aluminum coordination to the carbonyl groups within the polymers. In this context, two different reaction pathways are discussed. One deals with the formation of an acetal, the other is characterized by the release of a leaving group. Both were found to be in direct concurrence dependent on the polymer side group as revealed by DFT calculations of the IR spectra, as well as the reaction energies of two possible reaction paths. From this study, one can infer that the degree of infiltration in a VPI process strongly depends on the polymer side groups, which facilitates the choice of the polymer for targeted applications.

Regioselective synthesis of polysaccharide–amino acid ester conjugates

Site-specific conjugation of polysaccharides with proteins is very challenging. Creating the ability to control chemo- and regioselective reaction between polysaccharides and amino acid derivatives can not only create potentially useful and bioactive natural polymer constructs, but should also provide useful guidance for the principles of polysaccharide–protein conjugate synthesis. In this work, we exploited regioselective bromination of the non-reducing end primary dextran hydroxyl using N-bromosuccinimide (NBS) and triphenylphosphine (Ph3P) in the dimethylacetamide (DMAc) and lithium bromide solvent system, thereby enabling a regio- and chemoselective synthetic strategic approach to a variety of polysaccharide-amino acid ester adducts. We demonstrated selective condensation of the α-amino groups of esters of the amino acids tyrosine and proline, displacing the single, terminal C6 bromides of 6-BrDextran, as well as the 6-Br moieties of 6-BrCA320S, with high conversion (71–96%). Histidine ester side group amines were found to react with 6-BrCA320S, while those of tryptophan ester did not. These results provide useful access to polysaccharide–amino acid ester adducts of various architectures, and guide us in designing new pathways to polysaccharide–protein copolymers.

Tracking the complete degradation lifecycle of poly(ethyl cyanoacrylate): From induced photoluminescence to nitrogen-doped nano-graphene precursor residue

Poly(ethyl cyanoacrylate) (PECA) is a commercial polymer which degrades easily at temperatures between 150 - 200 °C via an unzipping reaction where volatile monomer is produced. In this report, the complete moderate-temperature degradation lifecycle is delineated, which also includes formation of a carbonaceous by-product where the ester side groups are lost and ring formation between the backbone and cyano side group occurs. Degradation-induced photoluminescence is observed at an intermediate point where the remaining PECA (or re-polymerized oligomers) has sp3 carbons but sp2-carbon-containing clusters of the by-product that will ultimately form aromatic structures are also present. This observation supports the hypothesis that degradation-induced photoluminescence in polymers, which has been observed widely, is connected to the formation of such sp2 containing clusters, and that this process is relatively independent of the original polymer chemistry, as PECA dominantly degrades through a mechanism distinctly different than the thermo-oxidative cascade associated with many thermoplastic materials. As degradation further advances, a residue of approximately 8% of the original mass is produced which is no longer photoluminescent and can ultimately transform into nitrogen-substituted nano-graphene. Observing the entire lifecycle further solidifies the previously-proposed connection between degradation-induced luminescence in polymers and photoluminescence in hydrogenated amorphous carbon. The low degradation temperature of PECA also provides a bridge between classic polymer degradation and waste-to-graphene strategies that generally involve much more aggressive processing.

Investigating the impact of regiochemistry in ester functionalized polyfurans

AbstractIn this study, the impact of ester side group regiochemistry on electronic and conformational properties of regioregular polyfurans was explored. A derivative with alternating head‐to‐head and tail‐to‐tail orientation of the side groups was synthesized and compared with its head‐to‐tail analogue, and these were benchmarked against the related regioregular poly(3‐hexylfurans). The study revealed that alkyl ester side groups in a head‐to‐head orientation will create significant steric strain as compared with linear alkyl chains with identical regiochemistry. Though the head‐to‐head ester side groups lead to twisting along the polymer backbone, they also produce a protective effect against photodegradation in comparison with a poly(3‐hexylfuran). Altogether, the work highlights how side groups can impact conformational properties and stability of polyfurans.

Microscopic simulation of e-beam induced PMMA chain scissions with temperature effect

This study presents microscopic quantitative model of e-beam induced poly-methylmethacrylate (PMMA) main-chain scissions. Scission processes are supposed to be caused by ester side group elimination, competing with hydrogen abstraction processes. Experimental values of PMMA radiation scission yield at different temperatures were obtained using direct Monte-Carlo algorithm for the simulation of e-beam scattering in PMMA/Si structure and detailed PMMA layer model for the simulation of exposed PMMA molecular weight distribution. The radiation scission yield increase at higher temperatures is associated by the increase of probability of remote PMMA main-chain scission, which follows the ester side group elimination. Temperature dependence of remote scission probability for the temperature range 20-180 °C is determined.

Tetrazole functional copolymers: Facile access to well-defined Rhenium(I)-Polymeric luminescent materials

Well-defined random copolymers containing tetrazole functional groups were prepared by a combination of reversible addition-fragmentation chain transfer (RAFT) radical homopolymerisation of pentafluorophenyl acrylate (PFPA), end-group modification and post-polymerisation modification of the activated ester side-groups with primary amines. PolyPFPA with a size exclusion chromatography (SEC) measured Mn of 10,800 and dispersity, Ð, of 1.05 was prepared with 2-cyano-2-propyl benzodithioate as the RAFT chain transfer agent and 2,2′-azobisisobutyronitrile (AIBN) as the source of primary radicals in 1,4-dioxane. Prior to modification of the pentafluorophenyl (PFP) ester side-groups, the thiocarbonylthio end-group was removed via a radical-mediated desulfurisation employing two equivalents of AIBN. Complete removal of the end-group was successful as judged by UV–vis spectroscopy with no effect on the molecular weight distribution of the parent homopolymer based on SEC analysis. The pendent PFP ester groups were subsequently modified in a sequential manner with n-butylamine and 5-aminotetrazole yielding the corresponding random amide species quantitatively, as judged by 19F NMR and FTIR spectroscopies, and of varying molar composition as determined by 1H NMR spectroscopy. The reaction of the tetrazole functional copolymers with Re(CO)3(phen)Br (phen = 1,10-phenanthroline) yielded the corresponding rhenium-polymer hybrids via coordination through the pendent tetrazole functional group. Successful, and quantitative coordination was confirmed by FTIR spectroscopy and detailed photophysical studies. In the case of the latter, the absorption profiles of all hybrid materials possessed broad bands centred around ca. 370 nm associated with metal-to-ligand charge transfer (MLCT) transitions; excitation as this wavelength results in a broad emission centred at 606 nm for all hybrid species and is due to emission from the triplet MLCT excited states.

Shedding Light on the Interactions of Hydrocarbon Ester Substituents upon Formation of Dimeric Titanium(IV) Triscatecholates in DMSO Solution.

The dissociation of hierarchically formed dimeric triple lithium bridged triscatecholate titanium(IV) helicates with hydrocarbyl esters as side groups is systematically investigated in DMSO. Primary alkyl, alkenyl, alkynyl as well as benzyl esters are studied in order to minimize steric effects close to the helicate core. The 1H NMR dimerization constants for the monomer–dimer equilibrium show some solvent dependent influence of the side chains on the dimer stability. In the dimer, the ability of the hydrocarbyl ester groups to aggregate minimizes their contacts with the solvent molecules. Due to this, most solvophobic alkyl groups show the highest dimerization tendency followed by alkenyls, alkynyls and finally benzyls. Furthermore, trends within the different groups of compounds can be observed. For example, the dimer is destabilized by internal double or triple bonds due to π–π repulsion. A strong indication for solvent supported London dispersion interaction between the ester side groups is found by observation of an even/odd alternation of dimerization constants within the series of n‐alkyls, n‐Ω‐alkenyls or n‐Ω‐alkynyls. This corresponds to the interaction of the parent hydrocarbons, as documented by an even/odd melting point alternation.

PH-Responsive Copolymer Films Prepared by Surface-Initiated Polymerization and Simple Modification.

We report the preparation of pH-responsive, ester/carboxylic acid random copolymer films via simple modification of poly(norbornene diacyl chloride) (pNBDAC), prepared via surface-initiated ring-opening metathesis polymerization, with mixtures of water and ethanol to form carboxylic acid and ethyl ester side groups. The pNBDAC film serves as a compositionally versatile platform to controllably obtain copolymers with multiple functionalities. In modifying the pNBDAC to form the copolymer film, ethanol exhibits a significantly higher reactivity with acyl chloride groups within the film than does water. The magnitude and range of the pH-responsive performance are highly dependent on the carboxylic acid content in the copolymer films, which demonstrates the effect of film hydrophilicity on the pH-responsive switching of ionic barrier properties. The resistance of the film against ion transfer can be decreased by a factor of 104 through pH change, demonstrating pH-induced switching from hydrophobic and insulating to swollen and ion-permeable films. The interactions of the copolymer films with water at different pH values were also explored. When the copolymer contains 34% carboxylic acids, a 4× greater film thickness is obtained in high pH solution than in low pH solution due to ionically driven water swelling. The reversibility of the pH-responsive performance of these copolymer films is high based on measurements using quartz crystal microbalance with dissipation (QCM-D).

Structure, Dynamics, and Apparent Glass Transition of Stereoregular Poly(methyl methacrylate)/Graphene Interfaces through Atomistic Simulations

We provide a detailed investigation of the structure and dynamics of stereoregular poly(methyl methacrylate) (PMMA) chains confined between graphene layers via atomistic molecular dynamics simulations. The density, conformation, and interfacial segmental dynamics of low molecular weight isotactic, syndiotactic, and atactic PMMA chains are examined at various temperatures, ranging from 490 K up to 580 K. For all stereoisomers, a tendency of chains to adsorb on graphene via ester-methyl groups is observed. Compared to other stereoisomers, isotactic chains are stretched and form better organized layers at the interface. Concerning dynamical properties, various dynamical modes of PMMA are studied as a function of distance from graphene as well as over the entire confined system. The interfacial backbone and ester side group motions are restricted, whereas the fast motion of methyl groups remains unaffected. In the temperature range studied here, the interphase thickness remains almost constant; however, the r...

Homopolymer and Random Copolymer of Polyhedral Oligomeric Silsesquioxane (POSS)-Based Side-Chain Polynorbornenes: Flexible Spacer Effect and Composition Dependence

A series of homopolymers and random copolymers of polyhedral oligomeric silsesquioxane (POSS)-based side-chain polynorbornenes were prepared using ring-opening metathesis polymerization. For the homopolymer P-z-POSS (z represents the spacer length, z = 5, 12, and 17), the POSS groups tethered to the side chain are linked to the polynorbornene backbone through the flexible spacer with different lengths. For the random copolymer P-6-co-17(X/Y) (X/Y = 1/1, 3/1, 6/1, and 9/1), the composition was regulated by adjusting the molar feed ratio X/Y of the norbornene monomer with butyl ester side group (M-6) to the POSS containing monomer with the longest spacer (M-17-POSS). Using various techniques, we studied the spacer length effect on POSS crystallization of the homopolymers and the composition dependence of physical properties of the copolymers. It is found that P-5-POSS is amorphous. On the contrary, POSS crystallization is observed in P-12-POSS and P-17-POSS, and the longer the spacer is, the higher the POSS...

Lipase-catalyzed synthesis of chiral poly(ester amide)s with an alternating sequence of hydroxy acid and l/d-aspartate units

Alternating poly(hydroxyhexanoic acid-alt-l/d-β-aspartate)s with α-benzyl or α-methyl ester side groups were prepared via the enzymatic polycondensation of N-(6-hydroxyhexanoyl) l/d-aspartate diesters.

エステル，ヒドロキシ基，メルカプト基を有するポリ(ジフェニルアセチレン)の合成および二酸化炭素透過性

エステル，ヒドロキシ基，メルカプト基を有するポリ(ジフェニルアセチレン)の合成および二酸化炭素透過性

Poly(methyl methacrylate) nanotubes in AAO templates: Designing nanotube thickness and characterizing the Tg-confinement effect by DSC

We used differential scanning calorimetry (DSC) to study the effect of confinement on the glass transition temperature (Tg) of poly(methyl methacrylate) (PMMA) nanotubes supported in anodic aluminum oxide (AAO) templates. We created nanotubes by wetting templates with polymer melts and developed a design equation relating tube thickness (ttube) with bulk radius of gyration (Rg): (ttube ≈ 2 Rg + 9 nm). The results indicate that ttube depends on overall conformation and size of the polymer coils and can be tuned at the nanoscale by polymer molecular weight. The Tg of AAO template-supported PMMA nanotubes increases with decreasing ttube, with Tg,tube − Tg,bulk = 12 K in 18-nm-thick nanotubes; we attribute the Tg increase to hydrogen bonds between PMMA ester side groups and hydroxyl groups on the surface of the γ-Al2O3 templates. Using ellipsometry, we characterized Tg-confinement effects for PMMA films supported on Si/SiOx, sputtered Al2O3 and sapphire (α-Al2O3). Films supported on substrates with higher concentrations of surface hydroxyl groups (α-Al2O3 > sputtered-Al2O3 > Si/SiOx) exhibit larger Tg-confinement effects. The DSC-determined Tg enhancements for nanotubes supported in γ-Al2O3 templates fall between the ellipsometry-determined Tg enhancements determined for PMMA films on α-Al2O3 and those for films on sputtered-Al2O3. These results show that molecular weight provides for tunability of polymer nanotube thickness in AAO templates, that there is excellent agreement in confinement effects measured by DSC and by ellipsometry, and that Tg can be tuned by modulating the levels of interfacial, polymer-substrate interactions by using surfaces with different chemical or crystallographic properties.

Inhibition of Marine Biofouling by Use of Degradable and Hydrolyzable Silyl Acrylate Copolymer

Silyl acrylate copolymers are promising materials for marine antibiofouling. However, their structures need optimizing to improve their erosion and mechanical properties. We have prepared copolymer of 2-methylene-1,3-dioxepane (MDO), tributylsilyl methacrylate (TBSM) and methyl methacrylate (MMA) via radical ring-opening copolymerization. Such polymer has a degradable backbone and hydrolyzable side groups. Our study demonstrates that as the ester units in the backbone increase, the degradation rate increases but the swelling decreases in seawater. The degradation is controlled by the polymer composition or the molar ratio of the ester units in the backbone to the silyl ester side groups. Moreover, such polymer can serve as a carrier and controlled release system for organic antifoulants. Marine field tests show that the system consisting of the copolymer and organic antifoulant has good antifouling performance depending on the polymer composition. It can effectively inhibit the colonization and growth of marine organisms when MDO content is above 20 wt %.

A combination of Electron Spin Resonance spectroscopy/atom transfer radical polymerization (ESR/ATRP) techniques for fundamental investigation of radical polymerizations of (meth)acrylates

This paper results from combining Electron Spin Resonance (ESR) spectroscopy and atom transfer radical polymerization (ATRP) to study the basic chemistry of radical polymerizations. This combination of analytical and controlled preparation techniques can provide information on chain length of propagating radicals and chain transfer reactions to polymers which has been previously difficult or impossible to study by direct detection of radicals in radical polymerizations by ESR.Two results are obtained by the ESR/ATRP combination technique. The first provides an estimation of the effect of chain length on the structure of methacrylate propagating radicals, especially in the initial stage of radical polymerizations. Model radical precursors of dimeric, trimeric, tetrameric, and pentameric structures of tBMA and MMA were prepared by ATRP. The corresponding model radicals were generated from these precursors and were observed by ESR at various temperatures. The ESR spectra provided direct information on chain length dependent changes of the averaged structures at the chain ends of the model propagating radicals, indicating that distortion in dihedral angles between chain end pπ-orbital and Cβ-H bonds increased with increasing chain length.The second result provides information on the radical migration reactions during the polymerization of acrylates. Radical precursors of ethyl-, n-butyl-, and dodecyl acrylates with various chain lengths (DP = 10, 25, 60, etc.) were prepared by ATRP. Model propagating radicals were generated from these precursors and were observed by ESR at various temperatures. These radicals showed chain length dependent spectroscopic change due to radical migration reactions from model propagating to mid-chain radicals with increasing temperature. Longer chained radicals with the same ester side groups showed easier formation of mid-chain radicals. An examination of side group dependency indicated that, longer alkyl side groups showed easier radical migration reactions. The development of ATRP enabled us to resolve these problems associated with side reactions in radical polymerizations.

Phosphonic acid‐containing polysulfones as anticorrosive layers

ABSTRACTAs a part of research work to elaborate polymeric materials for metal corrosion protection, we have developed a new family of phosphonic acid‐containing polymers. The synthesis and the characterization of polysulfones bearing alkyl phosphonate ester side groups are first described. These polymers are synthesized by direct polycondensation of a phosphonate ester‐containing bisphenol by aromatic nucleophilic substitution. The physicochemical properties of the resulting polymers are described. Acidic hydrolysis of phosphonate esters results in the formation of phosphonic acid groups. A series of phosphonic acid‐containing polysulfones is therefore obtained and characterized. A preliminary evaluation of the anticorrosive properties of these polymers is described. In 0.25M Na2SO4 solution, the corrosion rate of a polymer‐coated mild steel sample is much lower than of the free metal substrate. These results suggest that phosphonic acid‐containing polysulfones might be interesting as anticorrosive coatings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41890.