The 50 most-cited articles in Macromolecules, 2017

Abstract This Perspective summarizes the features and limitations of reversible addition–fragmentation chain transfer (RAFT) polymerization, highlighting its strengths and weaknesses, as our understanding of the process, from both a mechanistic and an application point of view, has matured over the past 20 years. It is aimed at both experts in the field and newcomers, including undergraduate and postgraduate students, as well as nonexperts in polymerization who are interested in developing their own polymeric structures by exploiting the simple setup of a RAFT polymerization.

It is likely that a half-century ago even enthusiastic and optimistic proponents of the synthetic polymer industry (Mr. McGuire included) could not have predicted the massive scale on which synthetic polymers would be manufactured and used today. Ultimately, the future success of this industry will rely on the development of sustainable polymers—materials derived from renewable feedstocks that are safe in both production and use and that can be recycled or disposed of in ways that are environmentally innocuous. Meeting these criteria in an economical manner cannot be achieved without transformative basic research that is the hallmark of this journal. In this Perspective we highlight five research topics—the synthesis of renewable monomers and of degradable polymers, the development of chemical recycling strategies, new classes of reprocessable thermosets, and the design of advanced catalysts—that we believe will play a vital role in the development of sustainable polymers. We also offer our outlook on several outstanding challenges facing the polymer community in the broad area of…

Abstract Membrane gas separation is a mature and expanding technology. However, the availability of better membrane materials would promote faster growth. In this Perspective we analyze the state of the art of membrane materials, including polymers and hybrid materials, as well as the current issues and barriers, and finally, we outline future research directions in membrane science. Development of new membrane materials for large scale separations will rely on a multidisciplinary approach that embraces the broad fields of chemical and materials engineering, polymer science, and materials chemistry.

The field of polymer nanocomposites has been at the forefront of research in the polymer community for the past few decades. Foundational work published in Macromolecules during this time has emphasized the physics and chemistry of the inclusion of nanofillers; remarkable early developments suggested that these materials would create a revolution in the plastics industry. After 25 years of innovative and groundbreaking research, PNCs have enabled many niche solutions. To complement the extensive literature currently available, we focus this Perspective on four case studies of PNCs applications: (i) filled rubbers, (ii) continuous fiber reinforced thermoset composites, (iii) membranes for gas separations, and (iv) dielectrics for capacitors and insulation. After presenting synthetic developments we discuss the application of polymer nanocomposites to each of these topic areas; successes will be noted, and we will finish each section by highlighting the various technological bottlenecks that need to be overcome to take these materials to full-scale practical application. By…

Polymer brushes have become a significant focus of polymer research with the need for straightforward and versatile surface modification. With the development of controlled radical polymerization from surfaces, new theoretical models, and sophisticated characterization tools, the resulting ability to control brush density and brush thickness gives unparalleled control over surface properties and functionality. By increasing brush density, a stretched brush conformation is formed as a result of constraining the cross-sectional area of that brush strand which thereby influences the interactions of molecules with the brush surface. The associated residual stress also gives polymer brushes properties distinct from an equivalent layer of coated polymer chains. Examples of uncharged and charged “grown from” polymer brushes, the effect of architecture on physical behavior, and the influence of nanoscale patterning will be described. The use of brush surfaces in biology relevant applications will be discussed and include resistance to nonspecific binding, cell bioadhesion, their use as…

From the beginning of life with the information-containing polymers until the present era of a plethora of water-based materials in health care industry and biotechnology, polyelectrolytes are ubiquitous with a broad range of structural and functional properties. The main attribute of polyelectrolyte solutions is that all molecules are strongly correlated both topologically and electrostatically in their neutralizing background of charged ions in highly polarizable solvent. These strong correlations and the necessary use of numerous variables in experiments on polyelectrolytes have presented immense challenges toward fundamental understanding of the various behaviors of charged polymeric systems. This Perspective presents the author's subjective summary of several conceptual advances and the remaining persistent challenges in the contexts of charge and size of polymers, structures in homogeneous solutions, thermodynamic instability and phase transitions, structural evolution with oppositely charged polymers, dynamics in polyelectrolyte solutions, kinetics of phase separation,…

Lignin derivative vanillin when coupled with diamines and diethyl phosphite followed by reaction with echichlorohydrin yields high-performance flame retardant epoxy resins. Biorenewable and environment-friendly flame retardant alternatives to bisphenol A epoxy resins (having plenty of applications such as coatings, adhesives, composites, etc.) have captured great attention due to their ecological and economic necessity. Vanillin, an industrial scale monoaromatic compound from lignin, is a promising sustainable candidate for high-performance polymers, while synthesis of diepoxies is challenging. Meanwhile, bio-based epoxy resins combining high performance and excellent fire resistance are more difficult to be achieved. In this paper, two novel bio-based epoxy monomers EP1 and EP2 were synthesized by one-pot reaction containing Schiff base formation and phosphorus–hydrogen addition between vanillin, diamines, and diethyl phosphite, followed by reacting with epichlorohydrin. Their reactivities are similar to bisphenol A epoxy resin DGEBA. After curing they showed excellent flame…

The development of facile and versatile strategies with low-cost for hydrogel construction is of tremendous scientific interest. Herein, we demonstrate that naturally derived, cost-effective tannic acid (TA) can be an efficient gelation binder for the hydrogel formation with a series of commercially available water-soluble polymers. With a five-polyphenol-arm structure, TA molecules are able to grasp polymer chains through either hydrogen or ionic bonds and cross-link them together by coordinate bonds in the presence of Fe(III) ions. These two interactions can be elegantly balanced by tuning the weight ratios of polymer/TA and TA/Fe 3+, which is the key point for the construction of supramolecular hydrogels. The supramolecular hydrogels exhibit multiple functionalities including mechanical tenability, rapid self-healing, pH-stimuli responsiveness, and free radical scavenging abilities. TA as a dynamic and versatile catechol group modifier provides a simple path to the construction of multifunctional hydrogels, which shows obvious advantages such as easy and green processing, low…

Soft polymer networks have seen an explosion of recent developments motivated by new high tech applications in the biomedical field or in engineering. We present a candid and critical overview of the current understanding of the relation between the structure and molecular architecture of polymer networks and their mechanical properties, restricting ourselves to soft networks made of flexible polymers and displaying entropic elasticity. We specifically review and compare recent approaches to synthesize swollen hydrogels with enhanced toughness, resilient but tough unfilled elastomers and self-healing networks containing dynamic bonds. The purpose is less to draw a comprehensive catalogue of approaches than to identify and unify the underlying principles controlling toughening mechanisms and mechanical self-healing behavior and to point out remaining challenges.

Conventional epoxy polymers are constructed by petro-based resources that are toxic and nonrenewable, and their permanent cross-links make them difficult to be reprocessed, reshaped, and recycled. In this study, a unique eugenol-derived epoxy (Eu-EP) is synthesized, and then vitrimeric materials are prepared by reacting Eu-EP with succinic anhydride (SA) at various ratios (1:0.5, 1:0.75, and 1:1) in the presence of zinc-containing catalysts. All vitrimers exhibit excellent shape changing, crack healing, and shape memory properties. Although vitrimers with 1:0.75 and 1:1 ratios cannot be physically reprocessed, they can be well reprocessed by the chemical method of being simply decomposed in a benign ethanol solution without loading additional catalyst. The collected decomposed polymers can form vitrimers again after exposure at 190 °C for 3 h. This work combines the concepts of vitrimer preparation, chemical recycling, and biobased polymer together, which would bring a feasible way to satisfy the demands of sustainability.

The translation of small molecule chemistries into efficient methodologies for polymer functionalization spans several decades, enabling critical advances in soft matter materials synthesis with tailored and adaptive property profiles. The present Perspective explores—based on selected examples—50 years of innovation in polymer functionalization chemistries. These span a diverse set of chemistries based on activated esters, thiol–ene/yne processes, nucleophilic systems based on isocyanates, reactions driven by the formation of imines and oximes, ring-opening processes, cycloadditions, and—in a recent renaissance—multicomponent reactions. In addition, a wide variety of chain types and architectures have been modified based on the above chemistries, often with exquisite chemical control, highlighted by key examples. We conclude our journey through polymer functionalization with the—in our view—most critically required advances that have the potential to move from “science fiction” to “science fact”.

The scope of this Perspective is to highlight innovative contributions in the synthesis of well-defined complex macromolecular architectures and to emphasize the importance of these materials to polymer physical chemistry, physics, theory, and applications. In addition, this Perspective tries to enlighten the past and show possible pathways for the future. Among the plethora of polymerization methods, we briefly report the impact of the truly living and controlled/living polymerization techniques focusing mainly on anionic polymerization, the mother of all living and controlled/living polymerizations. Through anionic polymerization well-defined model polymers with complex macromolecular architectures having the highest molecular weight, structural and compositional homogeneity can be achieved. The synthesized structures include star, comb/graft, cyclic, branched and hyberbranched, dendritic, and multiblock multicomponent polymers. In our opinion, in addition to the work needed on the synthesis, properties, and application of copolymers with more than three chemically different…

Abstract The ideal of living polymerization has defined research in polymer chemistry over the past 50 years. In this Perspective, we present the case that this concept has enabled the treatment of polymers as organic molecules, rather than impure mixtures of species, and allowed the translation of methods developed by synthetic organic chemists into ever more accessible living and/or controlled polymerization methods. The concurrent development of rapid analytical methods for screening new polymerization methods for living characteristics, chiefly size exclusion chromatography, has greatly aided in the expansion of living polymerization methods.

Single-ion conducting polymer electrolytes have been proposed to significantly enhance lithium ion battery performance by eliminating concentration gradients within the cell. Such electrolytes have universally suffered from poor conductivity at low to moderate temperatures. In an attempt to improve conductivity, numerous studies have sought to better understand the fundamental interplay of ion content and segmental motion, with typical analyses relying on a fit of temperature-dependent conductivity data using the Vogel–Tammann–Fulcher (VTF) equation to assist in separating these effects. In this study, we leverage the large accessible composition window of a newly synthesized, single ion conducting polysulfone–poly(ethylene glycol) (PSf- co -PEG) miscible random copolymer to more completely understand the interrelationship of glass transition temperature, ion content, and the polymer’s Li + conductivity. It is demonstrated here that choice of fitting procedure and Vogel temperature plays a crucial role in the observed trends, and importantly, after optimization of the data fitting…

Abstract It has been about 40 years since the field of organic conducting polymers was ignited by the demonstration of metallic conductivity in polyacetylene. A retrospective view of this research area suggests some areas remain ripe for discovery/innovation. The breadth of activities is too large to be comprehensive; hence, selected seminal, as well as some personal, contributions will be used to illustrate concepts and anecdotal ways to think about conducting polymer systems. This Perspective can serve as a tutorial for newcomers to the field and will also remind experts about results from the past. It begins with some history and simple views of electronic structure, with selected examples. Segmented polymers containing isolated redox units will be discussed as well as how these materials can be made to have high conductivity. Key examples illustrating the matching of redox potentials are transition metal hybrid structures. Interchain interactions are emphasized along with their role in determining the nature of the charges. Recent results that demonstrate dramatic…

This Perspective outlines recent advances concerning the formation and potential uses of block copolymer micelles, a class of soft-matter-based nanoparticles of growing importance. As a result of rapidly expanding interest since the mid-1990s, substantial advances have been reported in terms of the development of morphological diversity, structural complexity, control over micelle dimensions, scale-up, and applications in a range of areas from nanocomposites to nanomedicine.

High dielectric constant and low dielectric loss are desirable electrical properties for next-generation polymer dielectrics that show promise for applications in pulsed power, power electronics, and printable electronics. Unfortunately, the dielectric constant of polymers is often limited to 2–5, much lower than that of inorganic dielectrics, because of the nature of hydrocarbon covalent bonds for electronic and atomic polarizations. It is essential to understand the fundamental physics of different types of polarization and the associated loss mechanisms in polymers. In this Perspective, we discuss the characteristics of each polarization and explain how to enhance the polarization using rational molecular designs without causing significant dielectric losses. Among various approaches for high dielectric constant and low loss polymers, the multilayer film technology is of particular interest because a multilayer film is a unique one-dimensional system with tailored material choices, layer thicknesses, and interfaces. By minimizing the disadvantageous polarizations and enhancing…

Polyelectrolyte complexes, PECs, are spontaneously formed blends of polyelectrolytes bearing positive, Pol +, and negative, Pol –, repeat units. Many interesting PEC morphologies have been observed, ranging from dense precipitates to liquidlike coacervates to quasi-stable nanoparticles, depending on the identity of the polymers and the preparation conditions. While the number of polyelectrolytes available to synthesize these materials is large and increasing, the corresponding number of Pol + /Pol – combinations is vast. This work quantitatively compares the binding strengths between a selection of positive and negative polyelectrolytes by evaluating the extent to which ion pairs between them are broken by a common salt, KBr. Comparison of association constants or Gibbs free energies between different classes of ionic functionality reveals that more “hydrophilic” PECs are more weakly associated, small primary amines bind strongly, carboxylates bind weakly, and aromatic sulfonates interact more strongly than aliphatic ones. The use of “charge density” to predict binding strength is…

Dynamic covalent networks are polymer networks that contain a dynamic covalent bond which allows them to be reprocessable, remoldable, and recyclable as well as exhibit crack healing or stress-relaxation properties. A key component of these materials is the nature of the dynamic covalent bond, which in addition to chemical composition and architecture can be used to dramatically alter the physical properties of these networks. The aim of this study is to understand the impact of steric hindrance of N -alkyl substituents and network connectivity in poly(alkylurea–urethane) dynamic network films. In these materials, the dynamic bond is the hindered alkyl urea moiety, whose dynamic behavior is dictated by the sterics of the alkyl substituent. Networks were prepared by the noncatalyzed curing reaction of aminoethanol compounds of varying substituents with a trifunctional isocyanate cross-linker and varying amounts of a monofunctional capping agent. Thermomechanical properties and FTIR studies show the impact of hindered urea bond sterics on the reaction conversion, network connectivity,…

Development of thermally stable nickel-based catalysts is highly desirable for industrial gas-phase olefin polymerizations. On the basis of the strategy of promoting the thermostability of nickel catalyst by the ligand backbone, we herein reported novel dibenzobarrelene-derived α-diimine nickel precatalysts for ethylene polymerization. Increasing the steric bulk on the ligand backbone was expected to inhibit the N -aryl rotation of the α-diimine ligands by the repulsive interactions, thus enhancing thermal stability (100 °C) and living fashion a temperatures up to 80 °C. Bulk ligand backbone also improved tolerance of nickel catalyst toward polar groups, and the α-diimine nickel catalyst containing a 2,6- t Bu-dibenzobarrelene backbone catalyzed living copolymerization of ethylene and methyl 10-undecenoate.

The design of efficient radical photoinitiating systems requires a systematic and detailed evaluation of their photochemical characteristics. Correlating absorbance and the corresponding electronic transitions of a photoinitiator is critical for understanding its photoinduced reaction pathways. In the current contribution, we provide an in-depth investigation into the photochemistry and photophysics of two oxime ester derivatives ( O -benzoyl-α-oxooxime, OXE01, and O -acetyloxime, OXE02 ), known for their excellent performance in pigmented formulations. In particular, we shed light on their wavelength-dependent photopolymerization properties. We utilized a combination of UV–vis spectroscopy, density functional theory (DFT) calculations, photochemically induced dynamic nuclear polarization spectroscopy (photo-CIDNP), and pulsed-laser polymerization with a wavelength-tunable laser with subsequent size exclusion chromatography coupled to high-resolution electrospray ionization mass spectrometry (PLP-SEC-ESI-MS) for obtaining detailed insights. Both photoinitiators have high molar…

A novel difunctional benzoxazine with o -trifluoroacetamide functionality has been synthesized via Mannich condensation. The chemical structure of synthesized monomer has also been confirmed by 1 H, 13 C, and 19 F nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared (FT-IR) spectroscopy. The ring-opening polymerization of the resin and the subsequent conversion of the freshly generated polybenzoxazine into polybenzoxazole are studied by FT-IR and differential scanning calorimetry (DSC). In addition to the advantage of low polymerization temperature as other reported o -amide benzoxazines, the o -trifluoroacetamide benzoxazine also exhibits an unexpected lower benzoxazole formation temperature. Furthermore, the resulting fluorinated polybenzoxazole derived from the benzoxazine monomer possesses the combined excellent properties of facile synthesis, easy processability, low dielectric constant, high thermal stability, and long shelf life, evidencing its potential applications in microelectronic industries, aerospace, and other high-performance areas.

Poly(butylene terephthalate) (PBT) vitrimers were prepared by reactive extrusion from industrial PBT thermoplastics using Zn(II)-catalyzed addition and transesterification chemistry. PBT thermoplastics are characterized by a high degree of crystallinity, high melting temperature, and high crystallization rate, but right above their melting temperature their mechanical resistance disappears and they show a tendency to drip. We compared −OH and −COOH end-group additions on epoxies in the presence of two different catalysts: 2-methylimidazole (2-MI) and zinc acetylacetonate (Zn(acac) 2 ). With 2-MI, chain extension reactions were efficiently catalyzed in a few minutes at 270 °C, but no gelation was observed. With Zn(acac) 2, −COOH addition and transesterification led to efficient cross-linking within a few minutes at 270 °C. Such cross-linked material combines the crystalline properties of PBT and dimensional stability above the melting temperature. PBT materials cross-linked through epoxy-vitrimer chemistry are not soluble. However, compared with radiation cross-linked PBT, vitrimer…

Reinforcement, recycling, and functional applications are three important issues in elastomer science and engineering. It is of great importance, but rarely achievable, to integrate these properties into elastomers. Herein, we report a simple way to prepare covalently cross-linked yet recyclable, robust, and macroscopically responsive elastomer vitrimers by engineering exchangeable bonds into rubber–carbon nanodot (CD) interphase using CD as high-functionality cross-linker. The cross-linked rubbers can rearrange the network topology through transesterification reactions in the interphase, conferring the materials the ability to be recycled, reshaped, and welded. The relatively short chains bridging adjacent CD are highly stretched and preferentially rupture to dissipate energy under external force, resulting in remarkable improvements on the mechanical properties. Moreover, the malleable and welding properties allow the samples to access reconfigurable/multiple shape memory effects.

Anion exchange membranes (AEMs) are a promising class of materials that enable non-noble metals to be used as catalysts in fuel cells. Compared to their acidic counterparts, typically Nafion and other perfluorosulfonate-based membranes, the low OH – conductivity in AEMs remains a concern as these materials are developed for practical applications. Cross-linked macromolecular structures are a popular way to optimize the trade-off between the ionic conductivity and the water swelling of AEMs with high ion exchange capacities (IECs). However, common cross-linked AEMs (e.g., x (QH)QPPO) that have high degrees of cross-linking with low molecular weight between cross-links are usually mechanically brittle. Moreover, the cross-links in AEMs can hinder the transport of OH –, leading to unsatisfactory conductivities. Here we report a series of elastic and highly conductive poly(2,6-dimethylphenylene oxide) (PPO)-based AEMs ( x (QH) 3 QPPO) containing flexible, long-chain, multication cross-links. The strength and flexibility of the x (QH) 3 QPPO samples are significantly improved as compared…

The phenomenology of the glass transition and the associated behavior in the near liquid and glassy states are detailed, including the cooling rate dependence of the glass transition, Kovacs’ three signatures of structural recovery, and enthalpy overshoots. Dynamics in the liquid regime just above T g and the associated temperature dependences are also covered since this behavior is important to understanding the glassy dynamics. The current models of structural recovery and their shortcomings are presented. A number of important unanswered questions are discussed, including how the relaxation time in the glassy state depends on structure, the relationship between the evolution of different properties, the resolution of the Kauzmann paradox, and the behavior of the equilibrium relaxation time below T g . New experimental approaches are needed to make breakthroughs, such as two that are described: one involving 20 Ma amber to test whether the Vogel temperature dependence continues for the equilibrium state below T g and another involving an ideal polymer/pentamer mixture to obtain…

A simple and efficient approach to endow the controllable multi-stimuli-responsive property for the supramolecular polymer was successfully developed by rationally introducing iodine into a novel naphthalimide-functionalized pillar[5]arene-based supramolecular polymer (PNA⊃GBP). Interestingly, by introducing iodine into the supramolecular polymer PNA⊃GBP, the iodine could not only control the optical properties and self-assembly states of PNA⊃GBP via electronic donor–acceptor effect but also control the molecular recognition properties by competitive redox reaction. Benefiting from these excellent iodine controlled multiresponse properties, the PNA⊃GBP showed selective fluorescent response for cyanide, cysteine, and mercury in supramolecular polymer gels, water solutions, and living cells with high sensitivities. The supramolecular polymer PNA⊃GBP could act as a novel smart material for selective detection CN –, Hg 2+, and l -Cys.

Analyzing and understanding the structure and morphology of crystalline polymers has been and remains to be a major challenge. Some of the issues have resisted analyses for decades. The present account illustrates how individual contributions help build a body of knowledge that must cover length scales ranging from submolecular features to morphology and correlates them with bulk properties. Emphasis is put on structures and morphologies as formed spontaneously. Possible extension of the research area to connected fields is illustrated with a development on supramolecular crystals.

Hydrophobicity inherently affects a solutes behavior in water, yet how polymer chain hydrophobicity impacts aggregate morphology during solution self-assembly and reorganization is largely overlooked. As polymer and nanoparticle syntheses are easily achieved, the resultant nanoparticle architectures are usually attributed to chain topology and overall degree of polymerization, bypassing how the chains may interact with water during/after self-assembly to elicit morphology changes. Herein, we demonstrate how block copolymer hydrophobicity allows control over aggregate morphology in water and leads to remarkable control over the length of polymeric nanoparticle worms. Polymerization-induced self-assembly facilitated nanoparticle synthesis through simultaneous polymerization, self-assembly, and chain reorganization during a block copolymer chain extension from a hydrophilic poly( N, N -dimethylacrylamide) macro-chain-transfer agent with diacetone acrylamide and N, N -dimethylacrylamide. Slight variations in the monomer feed ratio dictated the block copolymer chain composition and were…

Abstract We report the preparation and structural and mechanical characterization of a tough supramolecular hydrogel, based exclusively on hydrophobic association. The system consists of a multiblock, segmented copolymer of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic dimer fatty acid (DFA) building blocks. A series of copolymers containing 2K, 4K, and 8K PEG were prepared. Upon swelling in water, a network is formed by self-assembly of hydrophobic DFA units in micellar domains, which act as stable physical cross-link points. The resulting hydrogels are noneroding and contain 75–92 wt % of water at swelling equilibrium. Small-angle neutron scattering (SANS) measurements showed that the aggregation number of micelles ranges from 2 × 102 to 6 × 102 DFA units, increasing with PEG molecular weight. Mechanical characterization indicated that the hydrogel containing PEG 2000 is mechanically very stable and tough, possessing a tensile toughness of 4.12 MJ/m3. The high toughness, processability, and ease of preparation make these hydrogels very attractive for applications where…

Over the past 30 years, atomic force microscopy (AFM) has played an important role in elucidating the structure and properties of polymer surfaces. AFM-based techniques have enabled the quantitative determination of the physicochemical properties of polymer surfaces with high spatial resolution and under a wide variety of conditions. Coupled with the improvements in spatial and temporal resolution, multiparametric and multifunctional characterization has revealed the delicate interplay between structure, dynamics, and properties at the surfaces of complex systems. Here we summarize some of the significant advances that have been made in synthetic polymeric materials, most in the past 10 years, where AFM has been crucial, and we provide our perspective on where AFM will be insightful in future and instrumental in advancing emerging areas.

New π-conjugated polymers with strong electron affinity, PNDTI-BBTs, consisting of naphtho[2,3- b:6,7- b ′]dithiophenediimide (NDTI) and benzo[1,2- c:4,5- c ′]bis[1,2,5]thiadiazole (BBT) units, were synthesized. PNDTI-BBTs have low-lying LUMO energy levels (∼−4.4 eV), which is sufficiently low for air-stable electron transport in organic field-effect transistors and for being readily doped by a well-known n-dopant, N, N -dimethyl-2-phenyl-2,3-dihydro-1 H -benzoimidazole ( N -DMBI), affording doped polymer films with relatively high conductivities and Seebeck coefficients. Depending on the solubilizing alkyl groups (2-decyltetradecyl, PNDTI-BBT-DT, or 3-decylpentadecyl groups, PNDTI-BBT-DP), not only the electron mobility in the transistor devices with the pristine polymer thin films (PNDTI-BBT-DT: ∼0.096 cm 2 V –1 s –1; PNDTI-BBT-DP: ∼0.31 cm 2 V –1 s –1 ) but also the conductivity and power factor of the doped thins films (PNDTI-BBT-DT: ∼0.18 S cm –1 and ∼0.6 μW m –1 K –2; PNDTI-BBT-DP: ∼5.0 S cm –1 and ∼14 μW m –1 K –2 ) were drastically changed. The differences in the electric…

The study of the conformation properties of macromolecules is at the heart of polymer science. Essentially all physical properties of polymers are manifestations of the underlying polymer conformations or otherwise significantly impacted by the conformation properties. In this Perspective, we review some of the key concepts that we have learned over nearly eight decades of the subject and outline some open questions. The topics include both familiar subjects in polymer physics textbooks and more recent results or not-so-familiar subjects, such as non-Gaussian chain behavior in polymer melts and topological effects in ring polymers. The emphasis is on understanding the key concepts, with both physical reasoning and mathematical analysis, and on the interconnection between the different results and concepts.

Abstract Molecular p-doping of the conjugated polymer poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) is a widely studied model system. Underlying structure–property relationships are poorly understood because processing and doping are often carried out simultaneously. Here, we exploit doping from the vapor phase, which allows us to disentangle the influence of processing and doping. Through this approach, we are able to establish how the electrical conductivity varies with regard to a series of predefined structural parameters. We demonstrate that improving the degree of solid-state order, which we control through the choice of processing solvent and regioregularity, strongly increases the electrical conductivity. As a result, we achieve a value of up to 12.7 S cm–1 for P3HT:F4TCNQ. We determine the F4TCNQ anion concentration and find that the number of (bound + mobile) charge carriers of about 10–4 mol cm–3 is not influenced by the degree of solid-state order. Thus, the observed increase in electrical conductivity by almost 2 orders…

As a promising alternative to thermoset elastomers, thermoplastic elastomers (TPEs) have attracted much attention because of their unique properties, including processability, reusability and recyclability. The synthesis of TPEs based on olefinic building blocks usually requires the use of long chain α-olefins, multiple steps, and/or multiple catalysts. The concept of using only ethylene as feedstock in a single step is fascinating but also very challenging. In this contribution, we report the synthesis of polyethylene-based TPEs through α-diimine nickel-catalyzed ethylene polymerization. The stress-at-break and strain-at-break values of these polyethylene products could be tuned over a very wide range using different nickel catalysts and different polymerization conditions. Most importantly, products with excellent elastic properties could be generated in the screening process.

Molecular weight distribution plays an important role by giving specific properties to polymeric materials. Despite the recent progress in controlled/“living” radical polymerization, polymer chemists do not have the ability to tune and manipulate the shape of molecular weight distributions (MWDs) (except for a few recent examples). In this article, new synthetic procedures have been developed for controlling MWDs using photoinduced electron/energy transfer–reversible addition-fragmentation chain transfer (PET-RAFT) polymerization, in conjunction with flow processes. By adjusting the pump flow rates, the chemical concentrations and residence times of the reactant streams were tailored throughout the polymerization, leading to control over the MWD. Changes to the intensity and wavelength of the light source also induced changes in the polymerization, allowing alteration of the MWD. The protocols described here should be amenable to a range of polymerization techniques and reaction setups.

Abstract Various carboxylic acid-functionalized poly(N,N-dimethylacrylamide) (PDMAC) macromolecular chain transfer agents (macro-CTAs) were chain-extended with diacetone acrylamide (DAAM) by reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization at 70 °C and 20% w/w solids to produce a series of PDMAC–PDAAM diblock copolymer nano-objects via polymerization-induced self-assembly (PISA). TEM studies indicate that a PDMAC macro-CTA with a mean degree of polymerization (DP) of 68 or higher results in the formation of well-defined spherical nanoparticles with mean diameters ranging from 40 to 150 nm. In contrast, either highly anisotropic worms or polydisperse vesicles are formed when relatively short macro-CTAs (DP = 40–58) are used. A phase diagram was constructed to enable accurate targeting of pure copolymer morphologies. Dynamic light scattering (DLS) and aqueous electrophoresis studies indicated that in most cases these PDMAC–PDAAM nano-objects are surprisingly resistant to changes in either solution pH or temperature. However, PDMAC40–PDAAM99…

The field of stimuli-responsive polymers has grown in the past three decades from a few obscure examples to one of the most vibrant domains of modern macromolecular science. Indeed, the research, development, and implementation of tailored materials that can respond in predefined ways to specific stimuli now cut across most areas in which “traditional” polymers play a role, and an ever-growing range of commercial products benefits from this class of materials. This Perspective is devoted to multistimuli, multiresponsive (MSMR) polymers, which are those materials that are able to respond to multiple, different stimuli with multiple, distinct responses. Somewhat akin to living systems, which have evolved to adapt and respond in complex ways to (combinations of) different environmental cues, MSMR polymers can offer a broad range of complex properties and functions. While much of the work on MSMR polymers has been devoted to the investigation of solutions or gels, this Perspective concentrates on solid materials, as this is the state of matter in which the vast majority of polymers are…

While it is known that the properties of polymer nanocomposites are largely dominated by the interfacial layer around nanoparticles, the molecular parameters controlling the interfacial layer structure and dynamics remain unknown. In this work we combine small-angle X-ray scattering, differential scanning calorimetry, and broadband dielectric spectroscopy to analyze the dependence of the interfacial layer thickness, l int, on polymer rigidity defined through the characteristic ratio, C ∞ . This analysis revealed a value of C ∞ ∼ 5–7, beyond which l int increases substantially with C ∞ . Moreover, l int grows upon approaching the glass transition temperature from above, and the rate of this growth seems to correlate with polymer fragility. Most important, our analysis revealed that l int is comparable to the characteristic length scale of dynamic heterogeneities in the studied materials. These results provide new understandings of molecular parameters controlling the interfacial layer and are important not only for the field of polymer nanocomposites but also for the fields of thin…

Abstract Development of living polymerizations via reversible activation of dormant species opened the door to discovery of metal-catalyzed living radical polymerization that is now very useful for precise construction of tailor-made polymeric architectures. In this commemorative Perspective, the historical aspects as well as the prospects as a new polymerization tool are described toward advanced structural control or technological materials innovation in various fields.

We use a combination of the coarse-grained molecular dynamics simulations and scaling analysis to study conformations of bottlebrush and comb-like polymers in a melt. Our analysis shows that a crossover between comb and bottlebrush regimes is controlled by the crowding parameter, Φ, describing overlap between neighboring macromolecules. In comb-like systems characterized by a sparse grafting of side chains (Φ < 1), the side chains and backbones belonging to neighboring macromolecules interpenetrate. However, in bottlebrushes with densely grafted side chains (Φ ≥ 1), the interpenetration between macromolecules is suppressed by steric repulsion between side chains. In this regime, bottlebrush macromolecules can be viewed as filaments with diameter proportional to size of the side chains. For flexible side chains, the crowding parameter is given by Φ ≈ [ v /( lb ) 3/2 ][( n sc / n g + 1)/ n sc 1/2 ], which depends on both the architectural parameters (degree of polymerization of the side chains, n sc, and number of backbone bonds between side chains, n g ) and chemical structure of…

A new type of semicrystalline vitrimer was prepared via the incorporation of glycerol into the amorphous phase of poly(butylene terephthalate) (PBT) by solid-state (co)polymerization (SSP). A near quantitative incorporation of the glycerol was confirmed by NMR spectroscopy. Wide-angle X-ray diffraction, differential scanning calorimetry (DSC), and temperature-modulated DSC showed that the PBT/glycerol-based vitrimers maintain the crystallization characteristics of normal PBT. By a change in the cross-link density of the PBT/glycerol-based vitrimers, a wide range of thermal, rheological and mechanical properties were obtained; e.g., the rubbery plateau modulus at 270 °C could be tuned from 0.07 to 3 MPa. The characteristic vitrimer behavior was demonstrated by stress relaxation and oscillatory frequency sweep experiments. In addition, these semicrystalline vitrimers can be recycled multiple times by compression molding without a substantial loss in dynamic mechanical and thermal properties.

High-throughput synthesis of well-defined polymer nano-objects has long been an attractive yet challenging topic in the area of polymer chemistry and material science. Herein, we report an enzyme-assisted photoinitiated polymerization-induced self-assembly (photo-PISA) approach to prepare well-defined AB diblock or ABC triblock copolymer nano-objects at room temperature in open vessels and multiwell plates. Kinetic studies indicated that the presence of glucose oxidase (GOx) endowed the polymerizations with excellent oxygen tolerance. Good control was maintained during the enzyme-assisted photo-PISA process. This method facilitates high-throughput PISA, allowing for the construction of a detailed phase diagram in a rather short time. We also demonstrate the potential bio-related application of this method by the successful encapsulation of horseradish peroxidase (HRP) and bovine serum albumin (BSA) into self-assembled polymer vesicles without compromising protein activities. This robust oxygen-tolerant PISA approach leads to unprecedented access to well-defined polymer nano-objects…

Abstract Microgels are colloidal-scale particles individually made of cross-linked polymer networks that can swell and deswell in response to external stimuli, such as changes to temperature or pH. Despite a large amount of experimental activities on microgels, a proper theoretical description based on individual particle properties is still missing due to the complexity of the particles. To go one step further, here we propose a novel methodology to assemble realistic microgel particles in silico. We exploit the self-assembly of a binary mixture composed of tetravalent (cross-linkers) and bivalent (monomer beads) patchy particles under spherical confinement in order to produce fully bonded networks. The resulting structure is then used to generate the initial microgel configuration, which is subsequently simulated with a bead–spring model complemented by a temperature-induced hydrophobic attraction. To validate our assembly protocol, we focus on a small microgel test case and show that we can reproduce the experimental swelling curve by appropriately tuning the confining sphere…

As Macromolecules celebrates its 50th anniversary, we reflect on the impact of polymer chemistry and engineering on the advancement of synthetic polymer fibers. In this Perspective, we focus on two exemplary cases: (i) high performance fibers and (ii) ultrafine electrospun fibers. High performance in this context refers to fibers like Kevlar and Spectra, which emerged as a consequence of novel chemistry and processing innovations to convert synthetic polymers into fibers with exceptional specific stiffness and strength. More recently, the development of “ultrafine” (i.e., submicrometer diameter) fibers by technologies such as electrospinning has advanced dramatically, resulting in interesting, emergent structures and properties, such as surface and internal morphologies, electrical and mechanical properties, and growth applications like tissue engineering and sensors, which are subjects of current research. In both cases, challenges and opportunities exist in the development of polymer processes to advance the current state of these synthetic polymer fibers.

Coordination insertion polymerization is unsurpassed as a straightforward method for synthesis of high-value polyolefins by the copolymerization of ethylene and polar monomers, but poison effects of polar groups on the metal center result in a lack of fine control over the polymer architecture. Herein we reported a thermally stable dibenzobarrelene-derived α-diimine palladium catalyst for the precision synthesis of functionalized polyolefins by living copolymerization of ethylene and a variety of acrylate comonomers. The introduction of the bulky dibenzobarrelene backbone can improve migratory insertion selectivity of methyl acrylate (MA) in a 2,1-mode, thus preventing polar groups from poisoning palladium centers by stable five-membered palladacycle intermediates formed by 1,2-insertion of MA. In this living chain-walking catalyst system, the composition, molecular weight, and branching topology of the copolymer can be facilely tunable by simple variation of the ethylene pressure.

Recently, many tough and self-healing hydrogels have been developed based on physical bonds as reversible sacrificial bonds. As breaking and re-forming of physical bonds are time-dependent, these hydrogels are viscoelastic and the deformation rate and temperature pronouncedly influence their fracture behavior. Using a polyampholyte hydrogel as a model system, we observed that the time–temperature superposition principle is obeyed not only for the small strain rheology but also for the large strain hysteresis energy dissipation and the fracture energy below a certain temperature. The three processes possess the same shift factors that obey the equation of Williams, Landel, and Ferry (WLF) time–temperature equivalence. The fracture energy Γ scales with the crack velocity V c over a wide velocity range as Γ ∼ V c α (α = 0.21). The exponent α of the power law is well-related to the exponent κ of the relaxation modulus G ( t ) ∼ t – κ (κ = 0.26), obeying the prediction α = κ/(1 + κ) from classic viscoelasticity theory. These results show that the fracture energy of the polyampholyte gel…

Polyelectrolyte complexes are a fascinating class of soft materials that can span the full spectrum of mechanical properties from low-viscosity fluids to glassy solids. This spectrum can be accessed by modulating the extent of electrostatic association in these complexes. However, to realize the full potential of polyelectrolyte complexes as functional materials, their molecular level details need to be clearly correlated with their mechanical response. The present work demonstrates that by making simple amendments to the chain architecture, it is possible to affect the salt responsiveness of polyelectrolyte complexes in a systematic manner. This is achieved by quaternizing poly(4-vinylpyridine) (QVP) with methyl, ethyl, and propyl substituents—thereby increasing the hydrophobicity with increasing side chain length—and complexing them with a common anionic polyelectrolyte, poly(styrenesulfonate). The mechanical behavior of these complexes is compared to the more hydrophilic system of poly(styrenesulfonate) and poly(diallyldimethylammonium) by quantifying the swelling behavior in…

The crystal structure model of stereocomplex between poly( l -lactic acid) (PLLA) and poly( d -lactic acid) (PDLA) with the L/D ratio of 50/50 was proposed by several groups [the space group P 1 model by Okihara et al. (1991) and R 3 c or R 3̅ c model by Cartier et al. (1997)], among which the model of the space group R 3 c (or R 3̅ c ) had been currently recognized as the most preferable one. However, the thus apparently established model cannot explain such an important experimental fact that the stereocomplex is formed not only for the PLLA/PDLA blend of the L/D ratio 50/50 but also for the blends with the L/D ratio of 70/30–30/70. We have proposed here a new model with the space group P 3, which can cover the SC structures of the L/D ratio in the range of 70/30–50/50–30/70. This model can show the more quantitative reproducibility of the observed X-ray diffraction data for both the hkl and 000 l reflection profiles. In particular the experimental observation of the 0003 reflection is inconsistent with the previous model of the space group R 3 c, which requests the appearance of…

N, N ′-Bicarbazole with almost spatially vertical structure was synthesized by a facile method and was demonstrated as a versatile building block for conjugated microporous polymers (CMPs) through transition metal catalyzed coupling polymerizations including Yamamoto, Suzuki, and Sonogashira polymerizations. The porosities and morphologies of four N, N ′-bicarbazole-based CMPs were systematically studied and compared. With high surface area, good thermal stability and microporous structure, the CMP synthesized by Yamamoto polymerization exhibited excellent adsorption capacities of CO 2 and organic dyes, and the maximum adsorption capacity of methylene blue (MB) in water reached up to 1016 mg g –1 . The good adsorption properties of N, N ′-bicarbazole CMPs could be a good candidate for potential applications in water purification and treatment.