A polarity‐activation strategy for the high incorporation of 1‐alkenes into functional copolymers via RAFT copolymerization

A new synthetic methodology for the preparation of copolymers having high incorporation of 1‐alkene together with multifunctionalities has been developed by polarity‐activated reversible addition‐fragmentation chain transfer (RAFT) copolymerization. This approach provides well‐defined alternating poly(1‐decene‐alt‐maleic anhydride), expanding the monomer types for living copolymerizations. Although neither 1‐decene (DE) nor maleic anhydride (MAn) has significant reactivity in RAFT homopolymerization, their copolymers have been synthesized by RAFT copolymerizations. The controlled characteristics of DE‐MAn copolymerizations were verified by increased copolymer molecular weights during the copolymerization process. Ternary copolymers of DE and MAn, with high conversion of DE, could be obtained by using additive amounts (5 mol %) of vinyl acetate or styrene (ST), demonstrating further enhanced monomer reactivities and complex chain structures. When ST was selected as the third monomer, copolymers with block structures were obtained, because of fast consumption of ST in the copolymerization. Moreover, a wide variety of well‐defined multifunctional copolymers were prepared by RAFT copolymerizations of various functional 1‐alkenes with MAn. For each copolymerization, gel permeation chromatography analysis showed that the resulting copolymer had well‐controlled M_n values and fairly low polydispersities (PDI = 1.3–1.4), and ¹H and ¹³C NMR spectroscopies indicated strong alternating tendency during copolymerization with high incorporation of 1‐alkene units, up to 50 mol %. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3488–3498, 2008     

Design and fabrication of a shielded interdigital sensor for noninvasive In situ real‐time production monitoring of polymers

Interdigital sensors (IDS) have received great attention for production monitoring of polymers over the past decade. However, conventional IDS are limited by high noise to environment due to the dual side access of the sensor, low nominal capacitance, and sensitivity. In this study, a shielded IDS fabricated by flexible circuit board (FCB) technology is presented to overcome these challenges. Compared to conventional sensors, the environmental dependence of the new sensor is minimized by the copper shield. Furthermore, nominal capacitance of at least 350% higher, and an increase of sensitivity per unit area are achieved. To demonstrate the capabilities of the new IDS, a FCB comprising the proposed sensor is fabricated, attached to a mould, and successfully applied for in situ real‐time production monitoring of an epoxy resin. The resulting flexible sensor is noninvasive towards the fabricated parts, and measures the key stages along the production process. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2028–2037     

Correction of Doi–Edwards' Green function for a chain in a harmonic potential and its implication for the stress‐optic rule

We show that the stress‐optic rule is violated in a theoretical model of polymer melts that uses a harmonic potential to confine a polymer chain in a tube‐like domain of surrounding entangled polymers. This is the model first proposed by Doi and Edwards (DE) [J. Chem. Soc. Farad. Trans. II 1978, 74, 1802] and later extended by Ianniruberto and Marrucci (IM) [J. Non‐Newton. Fluid Mech. 1998, 79, 225]. We first provide a rigorous Green function for such a chain, which is a correction to that derived by DE. The modification guarantees chain continuity. Second, we show that the stress‐optic rule is violated in the IM model if the modified Green function is used and an unnecessary assumption employed by IM is avoided. Our result contradicts that of IM. The violation is due to the presence of the virtual springs to confine the chain in the tube rather than the anisotropy of the confinement potential. On the other hand, DE used the virtual‐spring model only for estimation of the monomer density along the primitive path where we find just a small correction. As they did not use it for rheological calculations, the stress‐optic rule appears to be safe for the Doi–Edwards model. The result might be useful for extracting tube potentials from atomistic simulations. © 2014 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 460–469     

Stimuli‐responsive brush‐shaped conjugated polymers with pendant well‐defined poly(vinyl ether)s

For the synthesis of brush‐shaped conjugated polymers consisting of a poly(phenylene butadiynylene) backbone and well‐defined poly(vinyl ether) (polyVE) side chains, we designed polyVE‐based macromonomers bearing a diethynyl benzene group at the terminus and applied them to the grafting through synthesis. The macromonomer (DE‐PIBVE) was synthesized by living cationic polymerization of isobutyl VE (IBVE) using a functionalized initiator (TMS‐DEVE‐TFA) having a TMS protected diethynyl benzene moiety, followed by deprotection of the TMS groups. As a result, we succeeded in the synthesis of the target brush‐shaped conjugated polymers [poly(DE‐PIBVE)] by oxidative coupling reaction of the diethynyl benzene groups. We found that the solution of poly(DE‐PIBVE) with a specific side chain length exhibited solvatochromism and thermochromism depending on the polarity of the media employed. This phenomenon was attributed to self‐assembly in polar media due to the intermolecular π–π interaction between neighboring conjugated polymer backbones, where the self‐assembly behavior would be closely related to the pendant polyVE structure. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3318–3325     

Dielectric and rheological study of the molecular dynamics during the cure of an epoxy resin

Composite manufacturing is currently one of the most challenging processes for industrial lightweight applications. To date, the process conditions for polymer‐based composite manufacturing are evaluated by laboratory measurements: usually, the flow behavior and the curing of the polymer matrix material are characterized by rheology and quality assurance is performed by thermo‐physical analysis in postprocess measurements. In contrast a dielectric in‐mold sensor offers the possibility to measure the real‐time behavior of the polymer during processing. This study focuses on the correlation of simultaneous rheological and dielectric measurements on Hexcel RTM6 using a coupled setup of both techniques. For dielectric measurements a reusable in‐mold sensor was used and a calibration, taking into account the cable response, was performed. The results show good agreement with respect to glass‐transition temperature and the gel‐point. This can be understood by the fluctuation–dissipation theorem that explicitly relates molecular dynamics to the macromolecular mechanical properties under dynamic time‐dependent load. Furthermore, it was found that the dynamic viscosity can directly be related to the electrical conductivity. This proves the high potential of dielectric analysis as online‐capable technique for material characterization during composite manufacturing. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 907–913     

A helical chiral polymer‐based chromo‐fluorescence and CD response sensor for selective detection of trivalent cations

A novel chiral (S)‐BINAM‐based fluorescent polymer sensor was designed and synthesized by the polymerization of 4,4′‐((2,5‐dibutoxy‐1,4‐phenylene)bis(ethyne‐2,1‐diyl))‐dibenzaldehyde ( M‐1 ) with (S)‐2,2′‐binaphthyldiamine (S‐BINAM, M‐2 ) via Schiff's base formation. The resulting helical chiral polymer sensor exhibited remarkable “turn‐on” bright blue fluorescence color upon the addition of trivalent metal ions under a commercially available UV lamp; this change can be clearly observed by the naked eye for direct visual discrimination at low concentration. More importantly, the addition of trivalent metal cations can lead to a most pronounced change of CD spectra of the chiral polymer indicating this kind chiral sensor can also be used as a sole probe for selective recognition of trivalent metal cations based on CD spectra. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4070–4075     

The effect of concentration,temperature, and molecular weight on the dynamics of rigid-rod molecules in semi-dilute solutions

The dynamics of rigid-rod-like molecules are studied using rheo-optical techniques. Measurements of flow birefringence as a function of shear rate are utilized to understand the scaling behavior of rotational diffusivity with respect to concentration and temperature. The concentration scaling exponent increases with increasing concentration and the scaling laws are valid in narrow concentration windows. The Doi-Edwards (DE) scaling law D_r ∼ c⁻², holds at very high concentrations (cL³ > 150). The concentration scaling exponent decreases dramatically with increasing temperature at concentrations, cL²d > 1. Scaling of rotational diffusivity, with respect to temperature and solvent viscosity in the semidilute regime, does not follow the predictions of DE theory (and related caging ideas). On the contrary, a model proposed by Fixman was found to explain both the temperature and concentration dependence of the rotational diffusivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 181–190, 1998     

Polysiloxanes polymers with hyperbranched structure and multivinyl functionality

Hyperbranched polysiloxane polymers with multivinyl functionality were designed and synthesized through a “one‐step and one‐pot” deactivation enhanced atom transfer polymerization (DE‐ATRP) approach from the copolymerization of polydimethylsiloxane (PDMS) macromonomers and divinylbenzene (DVB). Various feed ratios of siloxane‐based monomer and divinyl monomers were investigated. We showed that even at DVB concentrations as high as 80 mol % in the feed, 65% yield of hyperbranched polymer could be obtained without gelation because the DE‐ATRP suppressed the rapid formation of macronetwork structures. The molecular weight, polydispersity, macromolecular structure of hyperbranched poly(DVB‐co‐PDMS) as well as its viscosity in silicone oil were characterized by GPC‐MALLS, ¹H NMR and rheometer. By tracking the relationship between the radius of gyration, elution volume and molecular weight from MALLS analysis, solid evidences of the highly branched and condensed structure of the polymers were obtained. Furthermore, the oil thickening experiments demonstrate that this hyperbranched polymer can act as a well‐controlled viscosity‐modifier for Silicone oils, which potentially will have important application in coating, cosmetic and pharmaceutical products. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesizing a new dielectric elastomer exhibiting large actuation strain and suppressed electromechanical instability without prestretching

Prestrain provides high actuation performance in dielectric elastomers (DEs) but increases the bulk, mass, and fatigue of the resulting actuators. Based on our experiments on prestrain‐locked interpenetrating polymer films and the model developed by Zhao and Suo, materials with a certain stress–strain relationship should be capable of high strain without prestrain by suppressing electromechanical instability (EMI). Here, we report the synthesis of an acrylic elastomer capable of achieving high actuation performance without prestrain. DE films were directly fabricated by ultraviolet curing of precursors comprising a mixture of acrylate comonomers. Varying the amount of crosslinker comonomer in the precursor allowed us to tune the stress–strain relationship and completely suppress EMI while maintaining high strain performance. Addition of plasticizing agents increased strain sensitivity. The result is a new DE, synthesized from scratch, capable of high actuation strain (>100%), high energy density (>1 J g^?1), and good temperature and frequency response without requiring prestretching. The material can be fabricated using conventional coating techniques and the process can allow for high volume throughput of stacked DE actuators. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Magnetic field-induced morphology-dependent resonances of a coupled composite metglas slab with a polymeric optical resonator

In this article, the effect of an external magnetic field on the morphology-dependent resonances (MDRs) of a polymeric dielectric microsphere is investigated. The microsphere is mechanically coupled to a composite polymeric Metglas slab. When an external magnetic field is applied to the slab, it elongates leading to a change in the morphology of the microsphere. This in turn leads to a shift in the excited optical resonances. Experiments are carried out to investigate the effect of an external static and harmonic magnetic field on the MDRs shift. The results show that this configuration can be used as an optical magnetic field sensor or as an optical tuning element. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 272–275     

The delocalisation energy of benzene and the non-empirical MO theory

Algebraic expressions for the vertical Delocalisation Energy (DE) of benzene are derived from non-empirical MO theory. For comparison with early work in the π-electron approximation, and ultimately with Hückel theory, the results are formulated in terms of a core resonance integral,β, and π-electronic repulsion integrals. All integral values are inferred from the results ofab initio SCF calculations. Two expressions are derived, which refer to two ways of forming the localised π MOs: one where three pairs of adjacent atomic orbitals are selected from a set of six orthogonalised orbitals; and another where a non-orthogonal set of atomic orbitals is used. The first expression is formally similar to an expression originally derived by Pople from a different point of view and with many approximations. This expression gives too large a magnitude for DE when used with anab initio value ofβ. The second expression gives a result much closer to an empirical value of DE and shows that the main reason for DE being about 50% of 2β rather than 2β is the stabilising effect of overlap in the localised structure, and that the less important factor is the inclusion of electronic repulsion.     

General description of the structure of branched polymers

A multidimensional distribution function is defined to describe the branching structure of branched homopolymers such as starch and polyacrylates. Averages of this function give distributions which can be measured using, for example, the number and weight distributions as a function of hydrodynamic volume from size‐exclusion chromatography and field‐flow fractionation, and two‐dimensional separation methods. This provides means to plot data to obtain physically meaningful quantities, and to test mechanistic postulates for the (bio)synthesis, of branched polymers. A simple enzyme‐kinetic model for a reduced form of this multidimensional distribution for starch biosynthesis is derived and solved. One application is to derive number distributions for the molecular weight distribution of debranched glycogen. Fitting this to experiment gives estimates of this ratio for two forms of glycogen. We propose that number distributions from size separation for starch (which, it is pointed out, are obtained directly from in‐line viscometric detection) have a simple and meaningful form when plotted as ln(number distribution) against V_h^p, where V_h is hydrodynamic volume, and p a parameter of order unity determined from multiple‐detection size separation measurements. The new function is also used to propose a two‐dimensional experiment which can yield an unambiguous measurement of the amylose: amylopectin ratio in starch. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3914–3930, 2009     

Multichannel detection using transmissive diffraction grating sensor

We report a novel transmissive diffraction grating pH sensor made of pH‐sensitive hydrogel. The sensor provides inherently multichannels for a flexible selection of different detection ranges, without involving any additional tuning mechanisms or using multiple sensing elements. Each transmitted diffraction order from the hydrogel grating forms an individual detection channel dedicated to a specific pH range. This unique feature is achieved, simply by enabling hydrogel ridges of the grating to swell effectively in lateral directions, while inhibiting the ridges from swelling in vertical direction and keeping grating period unchanged. Thus by looking at different diffraction orders and measuring their intensity ratio, it is possible to achieve tunable dynamic detection range. Besides, this approach can lead to a high‐sensitivity sensor for detecting subtle pH variations in a narrow pH range near the volume‐phase transition point of hydrogel, with the resolution at the level of 10^?3 pH units. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

The influence of hydrogen chloride doping level on the complex refractive indices of anisotropic polyaniline film: Application of a new internal reflection waveguide coupling technique

Nondestructive three‐dimensional refractive‐index measurements are used for the determination of both crystallinity and orientation in thin polymer films. The prism waveguide coupler is particularly suitable for three‐dimensional isotropic and anisotropic thin‐film studies because of the quantitative character of the information obtained and the ease of data acquisition. It has been limited, however, to measuring the refractive index of optically transparent or weakly absorbing films. This study shows that a modified prism waveguide coupler can be used to determine the complex refractive index over a range from transparent to highly absorbing films from the internally reflected light intensity. Thus, both the refractive index, n, and the extinction coefficient, k, can be obtained. This method is used to determine the anisotropic three‐dimensional n and k values of spin‐coated emeraldine base and hydrogen chloride doped emeraldine salt polyaniline films. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2481–2490, 2001     

Treating the polyelectrolytes as polymers with a draining effect. I. The statistical segment length

The statistical segment length of polyelectrolytes, A, in aqueous salt solutions is derived from the unperturbed dimensions parameter, K_θ, that is obtained from the graphical representations based on the Stockmayer–Fixman–Burchard and Dondos–Benoît equations. In order to obtain A from K_θ we use values of the Flory's parameter, Φ, which are given from an empirical equation established for the polymers presenting a draining effect, such as the wormlike polymers. With these values of Φ, the obtained values of A for different polyelectrolytes in aqueous salt solutions of different ionic strength are found very close to the values obtained from other more complicated methods. This result shows that the polyelectrolytes can be considered as polymers presenting a draining effect. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4225–4229, 2004     

Mechanical and electrical response variation of the polyurethane–tin oxide–carbon nanotube composite microfiber depending on the chemical solution

Toward the goal of smart sensor systems for wearable electronics, polymer microfiber‐based free‐standing sensors benefit from excellent flexibility, decent ductility, and easy wearability in comparison with thin‐film‐based sensing devices. Herein, we report a hydrophobic and conducting single‐strand microfiber‐based liquid‐phase chemical sensor consisting of polyurethane (PU), tin oxide (SnO₂), and carbon nanotube (CNT) composites with applying a (1H,1H,2H,2H‐heptadecafluorodec‐1‐yl) phosphonic acid (HDF‐PA)‐based self‐assembled monolayer. The free‐standing HDF‐PA‐treated PU–SnO₂–CNT composite microfiber showing selective filtering properties with the repellency of water and the penetration of an organic solvent is electrically and mechanically characterized. Finally, the single‐strand HDF‐PA‐treated PU–SnO₂–CNT composite microfiber‐based chemical sensor, which shows excellent mechanical properties and aqueous stability, is demonstrated to detect the presence of a chemical in pure water or counterfeit gasoline in pure gasoline by observing mechanical changes, especially variations in the length and diameter of the fiber, and monitoring the electrical resistance change. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 495–502     

On the interfacial energy of extended-chain crystals from polyethylene melt by revised Flory equations of fusion

To analyze extended-chain crystalline systems composed of linear polyethylene, Flory's conventional theory of fusion is reconsidered by introducing a new concept of crystallinity. When this new treatment is applied to a melting case of a low molecular weight polyethylene fraction (M_n = 5600) isothermally bulk crystallized, a certain result that very large lamellar thickness was caused by a very small increase in crystallization temperature can satisfactorily be explained by a significant change in interfacial free energy of the crystallite end. Further, it shows 14–17 kJ/mol as a nonequilibrium value range of interfacial free energy for highly crystalline polyethylene fractions of low molecular weight M_n ≦ 5600 by using the previous data presented by other workers. A similar result is also obtained on the M_n = 5600 fraction by analyzing from a standpoint of equilibrium crystallinity. In either case, the estimated range of interfacial free energy is consistent with the conventional range. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1293–1303, 1998     

Flexible triboelectric generator and pressure sensor based on poly[(R)‐3‐hydroxybutyric acid] biopolymer

The utilization of poly[(R)‐3‐hydroxybutyric acid] (PHB) biopolymer for a device that uses charging process in friction to convert mechanical energy into electric power is reported. The triboelectric generator (TEG) is fabricated by stacking a drop cast PHB film between indium tin oxide coated poly(ethylene terephthalate) (PET) and PET sheet. The charge transfer takes place through an established general rule according to which the material with higher dielectric constant becomes positively charged. Furthermore, the utilization of such TEG as pressure sensor is illustrated. TEGs have the potential of harvesting energy from touch screen, mechanical vibration, and more, with great applications in self‐powered sensors for heat and environmental monitoring and even large‐scale applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 859–863     

A Simple Colorimetric Au-on-Au Tip Sensor with a New Functional Nucleic Acid Probe for Food-borne Pathogen Salmonella typhimurium

An Au-on-Au tip sensor is developed for the detection of Salmonella typhimurium (Salmonella), using a new synthetic nucleic acid probe (NAP) as a linker for the immobilization of a DNA-conjugated Au nanoparticle (AuNP) onto a DNA-attached thin Au layer inside a pipette tip. In the presence of Salmonella, RNase H2 from Salmonella (STH2) cleaves the NAP and the freed DNA-conjugated AuNP can be visually detected by a paper strip. This portable biosensor does not require any electronic, electrochemical or optical equipment. It delivers a detection limit of 3.2×10³ CFU mL⁻¹ for Salmonella in 1 h without cell-culturing or signal amplification and does not show cross-reactivity with several control bacteria. Further, the sensor reliably detects Salmonella spiked in food samples, such as ground beef and chicken, milk, and eggs. The sensor can be reused and is stable at ambient temperature, showing its potential as a point-of-need device for the prevention of food poisoning by Salmonella.     

Monitoring of the shrinkage during the photopolymerization of acrylates using hyphenated photorheometry/near‐infrared spectroscopy

This article describes a new method for the quantitative determination and time‐resolved monitoring of the polymerization shrinkage during ultraviolet (UV) photopolymerization. It is based on rheometry using a modified oscillating rheometer. Shrinkage is determined from the decrease of the gap between the rheometer plates. Moreover, near‐infrared (NIR) spectra can be recorded directly in the rheometer, which allows continuous determination of the conversion at any time of a shrinkage measurement. As both shrinkage and conversion data come from the same experiment, shrinkage can be analyzed in dependence on the current conversion achieved during UV irradiation, which enables direct investigation of correlations between both parameters. Hyphenated photorheometry/FT‐NIR spectroscopy was used for the determination of the polymerization shrinkage of pure acrylate monomers and oligomers as well as acrylate‐based formulations. Quantitative shrinkage values were found to be in excellent correlation with data that were determined by an independent method (via buoyancy measurements) and data from literature. Furthermore, the effect of ambient and irradiation conditions or the content of nanoparticles on the degree of shrinkage was studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 729–739