Semi‐interpenetrating polymer networks based on crosslinked poly(N‐isopropyl acrylamide) and methylcellulose prepared by frontal polymerization

In this work, semi‐interpenetrating gels of poly(N‐isopropyl acrylamide) and methylcellulose were successfully synthesized by using the Frontal Polymerization (FP) technique. The gels were obtained in the presence of dimethyl sulfoxide and trihexyltetradecylphosphonium persulfate, as polymerization solvent and radical initiator, respectively, hence avoiding the formation of bubbles during polymerization. Then, some of the gels containing dimethyl sulfoxide were thoroughly washed with water, hence obtaining the corresponding hydrogels. The effects of the ratio between poly(N‐isopropyl acrylamide) and methylcellulose, the amount of crosslinker and solvent medium (i.e., dimethyl sulfoxide and water) were thoroughly studied, assessing the influence of temperature and velocity of FP fronts on the glass transition temperature values (dried samples), on the swelling behavior and on the dynamic‐mechanical properties (gels swollen both in water and dimethyl sulfoxide). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 437–443     

Photoinitiated polymerization of methacrylic monomers in a poly(methyl methacrylate) matrix: A comparative study with other matrices (styrene–butadiene–styrene,polystyrene, and polybutadiene)

The kinetics and mechanism of the photoinitiated polymerization of 1,6‐hexanediol dimethacrylate (HDDMA) in a poly(methyl methacrylate) (PMMA) matrix were studied. The maximum double‐bond conversion, the maximum polymerization rate, the intrinsic reactivity, and the kinetic constants for propagation and termination were calculated. For this system, a reaction‐diffusion termination mechanism occurred from the start of the polymerization, and it was predominantly maintained until high monomer concentrations, probably because of the relatively high intermolecular attraction force between the PMMA matrix and HDDMA monomer. In addition, a comparative study of the photoinitiated polymerization of methacrylic monomers in four different polymeric matrices [styrene–butadiene–styrene (SBS), polystyrene (PS), polybutadiene (PB), and PMMA] was carried out. The aggregation state, vitreous or rubbery, of the monomer–matrix system and the intermolecular strength of attraction in the monomer–matrix system and growing macroradical and matrix systems were the principal factors influencing the kinetic and mechanistic behavior of these systems. When PB and SBS were used as matrices, crosslinked polymerized products were obtained as a result of the participation of double bonds of the matrix in the polymerization process (copolymerization). PS sequences in the SBS and PS matrices also took part in the polymerization process through the coupling of the benzylic radical to the growing macroradical. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 120–127, 2002     

Photoinitiators with functional groups. VII. Covalently bonded camphorquinone—amines

Camphorquinone (CQ), a widely used photoinitiator (PI) in dental applications, was covalently bonded to aromatic amines to enhance the rate of electron and proton transfer effect due to the close vicinity of the diketone and the amine group. 10‐bromocamphorquinone and 10‐bromomethylcamphorquinone were selected as suitable precursors for esterification with the carboxyl group containing aromatic amines based on 4‐dimethylaminobenzoic acid. Properties of the new photoinitiating systems were investigated by UV spectroscopy and differential scanning photocalorimetry in lauryl acrylate. Compared to physical mixtures, in all cases similar or even better performance was obtained. Surprisingly, 10‐acetyl derivatives 7 – 9 and 18 especially, were found to be highly reactive. Compared to CQ/ethyl 4‐dimethylaminobenzoate, the rate of photopolymerization was increased by a factor of up to 2. Intramolecular reaction was confirmed by photo‐differential scanning calorimetry experiments with varying PI concentrations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4948–4963, 2004     

Miscibility and hydrogen‐bonding interactions in blends of carbon dioxide/epoxy propane copolymer with poly(p‐vinylphenol)

The miscibility and hydrogen‐bonding interactions of carbon dioxide and epoxy propane copolymer to poly(propylene carbonate) (PPC)/poly(p‐vinylphenol) (PVPh) blends were investigated with differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and X‐ray photoelectron spectroscopy (XPS). The single glass‐transition temperature for each composition showed miscibility over the entire composition range. FTIR indicates the presence of strong hydrogen‐bonding interassociation between the hydroxyl groups of PVPh and the oxygen functional groups of PPC as a function of composition and temperature. XPS results testify to intermolecular hydrogen‐bonding interactions between the oxygen atoms of carbon–oxygen single bonds and carbon–oxygen double bonds in carbonate groups of PPC and the hydroxyl groups of PVPh by the shift of C_1s peaks and the evolution of three novel O_1s peaks in the blends, which supports the suggestion from FTIR analyses. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1957–1964, 2002     

Optical and Calorimetrical Studies of Liquid Crystalline Materials Doped with Nanoparticles

Summary: Electro-optical properties of Polymer Dispersed Liquid Crystal (PDLC) films doped with different nanoparticles (NPs), as well as optical and morphological properties of liquid crystal/NP mixtures have been investigated. PDLC films were prepared by UV irradiation of thiol-ene monomers and liquid crystal E7 in the presence of a small amount (0.5 and 1 wt.%) of nanoparticles. The presence of NP strongly influence the properties of liquid crystal/NP mixtures. In particular, adding nanoparticles results in a decrease of the glass and nematic-isotropic transition temperatures of the LC, suggesting that strong interactions occur between LC and nanoparticles.     

Novel thermosets obtained by UV‐induced cationic copolymerization of DGEBA with an spirobislactone

The photocuring process of the diglycidyl ether of bisphenol A (DGEBA) with the bislactone 1,6‐dioxaspiro[4,4]nonane‐2,7‐dione (s(γ‐BL)) was studied. Triarylsulfonium hexafluoroantimonate was employed as photoinitiator. FTIR/ATR was used to study the evolution of epoxy, lactone, and intermediate spiroorthoester groups to identify the different reactions that take place during the photocuring process. Photo‐DSC and DSC were used to study the thermal evolution of the photocuring process and to assess the T_g of the fully cured material. Thermogravimetric analysis (TGA) was used to determine the thermal stability of the fully cured material. The thermomechanical properties of the materials were investigated using dynamic mechanical‐thermal analysis. Shrinkage undergone during photocuring and gelation was studied with TMA. A strong influence of the photocuring temperature on the photocuring process of the DGEBA‐ s(γ‐BL) system was observed. Differences in the reactivity of the different species were observed with respect to the thermally cured system using ytterbium triflate as cationic thermal initiator. As a consequence, photocured materials exhibited a superior thermal stability and lower flexibility. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5446–5458, 2007     

Photoinitiators with functional groups. VI. Chemically bound sensitizers

Several benzophenone‐ and thioxanthone‐based photosensitizers (PSs) were covalently bonded to hydroxyalkylphenone‐ and aminoalkylphenone‐based photoinitiators (PIs) to enhance the rate of the excitation‐transfer effect due to the close vicinity of the PS to the PI. The properties of these new systems were investigated with UV spectroscopy and photo‐differential scanning calorimetry. Broadband irradiation experiments and selective excitation of the PS were carried out for the physical mixtures and covalently bonded PI/PS combinations to investigate the effect of excitation transfer. Selective excitation of the PS chromophore revealed that the energy transfer was significantly increased in covalently bonded initiators in comparison with the physical mixtures. This effect was most pronounced for the hydroxyalkylphenones that were sensitized by suitable benzophenone derivatives, especially at low PI concentrations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2285–2301, 2004     

Nonisothermal crystallization behavior and crystalline structure of poly(3‐hydroxybutyrate)/layered double hydroxide nanocomposites

X‐ray diffraction method and differential scanning calorimetry analysis have been used to investigate the nonisothermal crystallization of poly(3‐hydroxybutyrate) (PHB)/poly(ethylene glycol) phosphonates (PEOPAs)‐modified layered double hydroxide (PMLDH) nanocomposites. Effects of cooling rates and PMLDH contents on the nonisothermal crystallization behavior of PHB were explored. These results show that the addition of 2 wt % PMLDH into PHB caused heterogeneous nucleation increasing the crystallization rate and reducing the activation energy. By adding PMLDH into the PHB probably hinder the transport ability of the molecule chains and result in a decreasing crystallity of PHB, thus increasing the activation energy. The correlation among melting behavior, apparent crystallite size, and paracrystalline distortion of PHB/PMLDH nanocomposites has been also discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 995–1002, 2007     

Synthesis and crosslinking of polyethers with nadimide derivative pendant groups

Polyethers with nadimide derivatives pendent groups have been prepared by ring-opening polymerization of nadimide glycidyl derivatives. The structure of the linear polymers has been confirmed by spectroscopic methods. Properties such glass transition temperatures and thermal resistance have been measured and related to their chemical structure. Crosslinking studies have been carried out by DSC and TGA. Kinetic parameters could be obtained by dynamic method. The crosslinking causes an increase in T_g of the system and it has been possible to relate this increase to the chemical structure of the network. © 1992 John Wiley & Sons, Inc.     

Free‐volume and crystallinity in low molecular weight poly(ethylene oxide)

Positron annihilation lifetime spectroscopy (PALS), differential scanning calorimetry, X‐ray diffraction, and polarized light optical microscopy were used to study six low molar mass poly(ethylene oxide) samples with average molar masses ranging from 1 × 10³ to 10 × 10³ g mol^?1. Dynamic light scattering was used to determine molar mass and polydispersity rigorously. Polymer samples with 70–95% crystallinity, which is an unusual range in PALS studies, were prepared by molten material quenching. The ortho‐positronium pick‐off lifetime (τ₃) and relative fractional free volume (f_v), determined by the free volume model, correlated well with the average molar mass and crystallinity of the polymers. X‐ray diffraction and polarized light optical data support the interpretation of positron annihilation results. PALS parameter, I₃, which is associated with high cavity content, remained approximately constant at 20–22% for all samples. The cavities are present as crystallite defects in the spherulitic open texture and the amorphous phase for the low crystallinity sample (e.g., for M_w = 1390) and at the interfaces and in interlamellar spherulite regions of the more crystalline materials. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2400–2409, 2007     

Influence of the initiating mechanism on the cationic photopolymerization of a cycloaliphatic epoxy resin with arylsulfonium salts

The photocuring process of widely used 3,4‐epoxycyclohexylmethyl 3′,4′‐epoxycyclohexane carboxylate has been investigated with differential scanning photocalorimetry and attenuated total reflection/Fourier transform infrared. Mixed salts of triarylsulfonium hexafluoroantimonate have been employed as the photoinitiator. The photocuring of the biscycloaliphatic resins exhibits a complex behavior: the overall heat of reaction (including dynamic thermal postcuring) depends on the photocuring temperature, surprisingly high reaction rates are observed at lower photocuring temperatures, and the range of the glass transition of the fully cured material broadens and shifts to higher temperatures as the photocuring temperature increases. It is assumed that the balance between the initiation step and the propagation step is responsible for the changes in the reaction mechanism that produce the observed experimental results. This balance may depend on the amount of the photoinitiator, the irradiation intensity, and the photocuring temperature. The structure and final properties of the material may therefore depend on the adjustment of these parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 16–25, 2007     

Photoinitiators with functional groups. V. New water‐soluble photoinitiators containing carbohydrate residues and copolymerizable derivatives thereof

The synthesis of new water‐soluble photoinitiators (PIs) based on hydroxyalkylphenones, benzophenones, and thioxanthones with carbohydrate residues such as glucose, cellobiose, and 1‐amino‐1‐deoxy‐D ‐glucitol (glucamine) is described. In addition, selected initiators were reacted with methacryloyl chloride to obtain copolymerizable initiators with improved migration stability. Results from photo differential scanning calorimetry and gel‐content measurements in commercially available water‐thinnable and emulsion‐type resins as well as 2‐hydroxyethyl acrylate are included. Glucose‐modified PIs gave the best results with respect to compatibility with the resin, reactivity, and gel content. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1504–1518, 2002     

Polymer crystalline structure and morphology changes in nylon‐6/ZnO nanocomposites

The influence of ZnO nanoparticles on the crystalline structures of nylon‐6 under different crystallization conditions (annealing at different temperatures from the amorphous solid, isothermal crystallization from the melt at different temperatures, and crystallization from the solution) has been examined with differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction, field emission scanning electron microscopy, and Fourier transform infrared. ZnO nanoparticles can induce the γ‐crystalline form in nylon‐6 when it is cooled from the melted state and annealed from the amorphous solid. This effect of ZnO nanoparticles increases with decreasing particle size and changes under different crystallization conditions. The effects of ZnO nanoparticles on the crystallization kinetics of nylon‐6 have also been studied with DSC. The results show that ZnO nanoparticles have two competing effects on the crystallization of nylon‐6: inducing the nucleation but retarding the mobility of polymer chains. Finally, the melting behavior of the composites has been investigated with DSC, and the multiple melting peaks of composites containing ZnO nanoparticles and pure nylon‐6 are ascribed to the reorganization of imperfect crystals. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1033–1050, 2003     

Immiscible polydiene blocks in linear copolymer and terpolymer sequences

Synthesis, molecular, and morphological characterization of two linear diblock copolymers consisting of two polydienes with specific geometric isomerisms and two triblock terpolymers with a combination of the same polydienes with polystyrene are investigated for both lower and very high molecular weights. This work is inspired from a previous research study which demonstrated that linear ABC terpolymers consisting of polystyrene, poly(butadiene), and poly(isoprene), with specific geometric isomerisms for the polydienes, lead to 3‐phase microphase separated systems. We report also the coexistence of the core‐shell double gyroid and the 3‐phase 4‐layer alternating lamellae morphologies with the majority fraction being the lamellar structure. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1238–1246     

Calculation of smoothing factors for the comparison of DSC results

Complex mixtures of long chain organic compounds often show overlapping glass transition temperatures (T _gs) when analyzed by differential scanning calorimetry (DSC) or modulated DSC (MDSC). In such cases, subjective and inconsistent smoothing of data acquired under different conditions can lead to the misinterpretation of results. A quantitative method for the selection of smoothing factors for the analysis and comparison of (M)DSC results is presented. The method is most useful for the analysis of the derivative of the heat capacity, dC _p/dt or dC _p/dT, plots which best highlight overlapping T _gs. Four equations are shown to relate the heating rate and the smoothing factor. The equations allow a comparison of data acquired i) at different heating rates and plotted vs. temperature, ii) at a single heating rate and plotted vs. both time and temperature, i.e., dC _p/dt vs. dC _p/dT, iii) at different heating rates and plotted vs. both time and temperature, and iv) at different heating rates, and shown exclusively in the time domain. Examples of the use of the equations are provided for the analysis of bitumen, a complex mixture of natural origin.     

One‐ and two‐photon activity of cross‐conjugated photoinitiators with bathochromic shift

Intrigued by the good performance of 1,5‐diphenylpenta‐1,4‐diyn‐3‐one ( DPD ) as photoinitiator for radical polymerization we prepared and investigated several donor substituted derivatives. UV‐Vis spectroscopy revealed a gradual red‐shift of λ_max and higher extinction in the order of the donor capability. A methoxy‐substituted derivative ( O‐DPD ) exhibited significant photoinitiation activity in photo‐DSC experiments. Steady state photolysis experiments showed decreased decomposition rates with increasing donor capability. A dimethylamino derivative N‐DPD was even photostable under these conditions. Because of to the D‐π‐A‐π‐D system of these compounds two‐photon induced 3D photopolymerization experiments were performed and N‐DPD showed outstanding performance compared to often applied single photon initiators. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3280–3291, 2007     

Competition between supernucleation and plasticization in the crystallization and rheological behavior of PCL/CNT‐based nanocomposites and nanohybrids

PCL was blended with pristine multiwalled carbon nanotubes (MWCNT) and with a nanohybrid obtained from the same MWCNT but grafted with low molecular weight PCL, employing concentrations of 0.25 to 5 wt % of MWCNT and MWCNT‐g‐PCL. Excellent CNT dispersion was found in all samples leading to supernucleation of both nanofiller types. Nanohybrids with 1 wt % or less MWCNTs crystallize faster than nanocomposites (due to supernucleation), while the trend eventually reverses at higher nanotubes content (because of plasticization). Rheological results show that yield‐like behavior develops in both nanocomposites, even for the minimum content of carbon nanotubes. In addition, the MWCNT‐g‐PCL family, when compared with the neat polymer, exhibits lower values of viscosity and modulus in oscillatory shear, and higher compliance in creep. These rheological differences are discussed in terms of the plasticization effect caused by the existence of low molecular weight free and grafted PCL chains in the nanohybrids. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1310–1325     

Polydispersity of ethylene sequence length in metallocene ethylene/α‐olefin copolymers. II. Influence on crystallization and melting behavior

In this work, crystallization and melting behavior of metallocene ethylene/α‐olefin copolymers were investigated by differential scanning calorimetry (DSC) and atomic force microscopy (AFM). The results indicated that the crystallization and melting temperatures for all the samples were directly related to the long ethylene sequences instead of the average sequence length (ASL), whereas the crystallization enthalpy and crystallinity were directly related to ASL, that is, both parameters decreased with a decreasing ASL. Multiple melting peaks were analyzed by thermal analysis. Three phenomena contributed to the multiple melting behaviors after isothermal crystallization, that is, the melting of crystals formed during quenching, the melting‐recrystallization process, and the coexistence of different crystal morphologies. Two types of crystal morphologies could coexist in samples having a high comonomer content after isothermal crystallization. They were the chain‐folded lamellae formed by long ethylene sequences and the bundlelike crystals formed by short ethylene sequences. The coexistence phenomenon was further proved by the AFM morphological observation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 822–830, 2002     

Dynamic mechanical behavior of acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) blends

The dynamic mechanical behavior of uncrosslinked (thermoplastic) and crosslinked (thermosetting) acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) (NBR/EVA) blends was studied with reference to the effect of blend ratio, crosslinking systems, frequency, and temperature. Different crosslinked systems were prepared using peroxide (DCP), sulfur, and mixed crosslink systems. The glass‐transition behavior of the blends was affected by the blend ratio, the nature of crosslinking, and frequency. sThe damping properties of the blends increased with NBR content. The variations in tan δ_max were in accordance with morphology changes in the blends. From tan δ values of peroxide‐cured NBR, EVA, and blends the crosslinking effect of DCP was more predominant in NBR. The morphology of the uncrosslinked blends was examined using scanning electron and optical microscopes. Cocontinuous morphology was observed between 40 and 60 wt % of NBR. The particle size distribution curve of the blends was also drawn. The Arrhenius relationship was used to calculate the activation energy for the glass transition of the blends, and it decreased with an increase in the NBR content. Various theoretical models were used to predict the modulus of the blends. From wide‐angle X‐ray scattering studies, the degree of crystallinity of the blends decreased with an increasing NBR content. The thermal behavior of the uncrosslinked and crosslinked systems of NBR/EVA blends was analyzed using a differential scanning calorimeter. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1556–1570, 2002