Effects of ultrasonic oscillations on linear viscoelastic behaviors of metallocene‐catalyzed linear low density polyethylene and its blends with low density polyethylene

The effects of ultrasonic oscillations on linear viscoelastic behaviors of metallocene‐catalyzed linear low density polyethylene (mLLDPE) and its blends with low density polyethylene (LDPE) were investigated in this article. The experimental results showed that ultrasonic oscillations can increase the cross modulus, characteristic time, plateau modulus, complex viscosity, zero shear viscosity, and flow activation energy of mLLDPE. Molecular weight of mLLDPE increases but molecular polydispersity index decreases in the presence of ultrasonic oscillations. It has been found for mLLDPE/LDPE blends that the addition of LDPE as well as ultrasonic oscillations can decrease the cross modulus but increase the characteristic time of the blends. The complex viscosity, zero shear viscosity, and flow activation energy of the blends increase by the addition of LDPE, but decrease in the presence of ultrasonic oscillations. Shear thinning effect of the blends is improved because of the addition of LDPE. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3030–3043, 2005     

Effect of LDPE on the thermomechanical properties of LLDPE‐based films

The present study compares the properties of five films: one film of low‐density polyethylene (LDPE), two films of linear low density polyethylenes (1‐octene comonomer)—one made by metalllocene catalyst (mLLDPE) and the other by Ziegler–Natta (zLLDPE)—and two blend films, one of mLLDPE/LDPE (film A) and the other of zLLDPE/LDPE (film B). The effect of LDPE (22% by weight) on the thermomechanical properties of LLDPE‐based films is investigated by using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and stress‐strain in the yield region measurements. The mechanical, dynamic, and thermal properties of film A are quite similar to a single component system (mLLDPE). The addition of this amount of LDPE does not affect the melting temperature of mLLDPE but it enhances its crystallinity. Film B is a rather inhomogeneous material, as opposed to film A, and its properties seem to be dependent on stretching conditions. Furthermore, the thermally activated rate process (Eyring's theory) is applied to analyze the yielding behavior of the two blend films. Double yielding manifested by film B is described with two thermally activated processes, while film A is satisfactorily described by a single process. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1712–1727, 2005     

High‐power ultrasonic treatment of butyl rubber gum: Structure and properties

The ultrasonic treatment of butyl rubber gum during extrusion with a grooved‐barrel ultrasonic reactor was carried out at a mean residence time of 3.6 s and at different ultrasonic amplitudes. Gel permeation chromatography, NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and dynamic and mechanical property measurements were performed. The changes in the structure, curing behavior, and physical properties of the gum were found to be highly dependent on the applied ultrasonic amplitude. In particular, the molecular weight of the treated gum decreased and the molecular weight distribution increased with the ultrasonic amplitude. The number of double bonds in the ultrasonically treated gum was less than that in the virgin gum. The dynamic properties of the ultrasonically treated gums also indicated the occurrence of degradation during the ultrasonic treatment. The tensile strength and modulus of the vulcanizates prepared from the treated gums were reduced in comparison with those of the virgin vulcanizate because of degradation. In contrast, the elongation at break was higher. However, no significant changes in the thermal stability between the virgin and treated gums and among the vulcanizates were observed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 334–344, 2005     

Modeling of the linear viscoelastic behavior of low‐density polyethylene

We predict the linear viscoelastic behavior of low‐density polyethylene from both the molecular‐weight distribution and the individual structure of each species in the sample. The “structure map” of the samples was derived from SEC measurements. This map is a three‐dimensional representation of the seniority distribution, and represents the probability of existence of a segment with seniority i in a molecule of molecular weight M. Moreover, results from the kinetics of the free radical polymerization of polyethylene show that the molecular weight of the segments increases according to their seniority. Finally, tube dilatation was generalized to the case of polydisperse samples. The solvent behavior of the relaxed segments was included through a continuous function of time that describes the instantaneous state of the entanglement network in the sample. The comparison between the theoretical predictions and the experimental data shows a good agreement over the whole experimental frequency range. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43:1973–1985, 2005     

IMPROVED PROPERTIES OF METALLOCENE-CATALYZED LINEAR LOW-DENSITY POLYETHYLENE/POLYPROPYLENE BLENDS DURING ULTRASONIC EXTRUSION

Metallocene-catalyzed linear low-density polyethylene/polypropylene （mLLDPE/PP） blends were prepared by ultrasonic extrusion in this work. Their extrusion processing behaviors were estimated by online measured data, such as the die pressure and flow rate. Crystallization and mechanical properties of the blends were also investigated. The results show that the addition of PP improves the processing behaviors of mLLDPE, but has little effect on its mechanical properties. On the other hand, the addition of mLLDPE improves the impact strength of PP, but has little effect on its processing behavior. The processing behaviors and mechanical properties of mLLDPE/PP blends get further improved due to the presence of ultrasonic oscillation during extrusion. Compared with PP-rich blends, the apparent viscosity drop of mLLDPE-rich blends is more sensitive to ultrasonic oscillation. The ultrasonic oscillation affects the crystal nucleation, while barely the other crystalline behaviors of the blends.     

Synthesis of well‐defined three‐armed polystyrene having thiourethane–isocyanurate as the core structure derived from trifunctional five‐membered cyclic dithiocarbonate

The synthesis of a three‐armed polymer with an isocyanurate–thiourethane core structure is described. Monofunctional reversible addition–fragmentation chain transfer (RAFT) agent 2 and trifunctional RAFT agent 5 were prepared from mercapto‐thiourethane and tris(mercapto‐thiourethane), which were obtained from the aminolysis of mono‐ and trifunctional five‐membered cyclic dithiocarbonates, respectively. The radical polymerization of styrene in the presence of 2,2′‐azobis(isobutyronitrile) and RAFT agent 2 in bulk at 60 °C proceeded in a controlled fashion to afford the corresponding polystyrene with desired molecular weights (number‐average molecular weight = 3000–10,100) and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.13). On the basis of the successful results with the monofunctional RAFT agents, three‐armed polystyrene with thiourethane–isocyanurate as the core structure could be obtained with trifunctional RAFT agent 5 in a similar manner. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5498–5505, 2005     

Linear viscoelastic properties of high‐density polyethylene/polyamide‐6 blends extruded in the presence of ultrasonic oscillations

Blends of high‐density polyethylene (HDPE) and polyamide‐6 (PA6) were produced by ultrasonic extrusion. Ultrasonic irradiation leads to degradation of polymers and in situ compatibilization of blends as confirmed by variations in linear viscoelastic properties. The results showed that the effect of ultrasonic irradiation on dynamic rheological properties depends on the composition and experimental temperature. At the same time, the relationship between storage modulus and loss modulus indicated the effect of ultrasonic irradiation on compatibility of HDPE/PA6 blends. Based on an emulsion model, the interfacial tension between the matrix and the dispersed phase was predicted. The data obtained showed that ultrasonic irradiation can decrease the interfacial tension and then enhance the compatibility of HDPE/PA6 blends. This finding was consistent with our previous work. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1260–1269, 2005     

Block and random copolymers as surfactants for dispersion polymerization. I. Synthesis via atom transfer radical polymerization and ring‐opening polymerization

Atom transfer radical polymerization (ATRP) and ring‐opening polymerization (ROP) were combined to synthesize poly(?‐caprolactone‐co‐octadecyl methacrylate‐co‐dimethylaminoethyl methacrylate) copolymers possessing a triblock or random block structure. Various synthetic pathways (sequential or simultaneous approaches) were investigated for the synthesis of both copolymers. For the preparation of these copolymers, an initiator with dual functionality for ATRP/anionic ring‐opening polymerization, 2‐hydroxyethyl 2‐bromoisobutyrate, was used. Copolymers were prepared with good structural control and low polydispersities (weight‐average molecular weight/number‐average molecular weight < 1.2), but one limitation was identified: the dimethylaminoethyl methacrylate (DMAEMA) block had to be synthesized after the ?‐caprolactone block. ROP could not proceed in the presence of DMAEMA because the complexation of the amine groups in poly(dimethylaminoethyl methacrylate) deactivated tin(II) hexanoate, which was used as a catalyst for ROP. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1498–1510, 2005     

Solid‐state polymerization of 2,3,6,7,10,11‐hexa(methacrylate) triphenylene

A new monomer, 2,3,6,7,10,11‐hexa(methacrylate) triphenylene (HMTP), and its crystals have been successfully synthesized, and the solid‐state polymerization under UV irradiation has been investigated. The photo polymerization of HMTP in solid was confirmed by the reduction of vinyl bonds in the FT‐IR and UV spectra of PHMTP in comparison with the corresponding spectra of its precursor. Thus, IR spectroscope was used to follow the polymerization of HMTP crystals under UV irradiation, and kinetic studies show a first‐order reaction with rate constant of 6.12 × 10^?3 min^?1. This value is slightly larger than that measured by the weight method. The polarizing optical microscope and X‐ray diffraction were used to study the crystal structure difference between the polymers and its monomer. The results show that the polymers' crystals obtained from photo polymerization kept the monomer crystal lattice. Because of strong overlap between the π‐electron of the triphenylene, the monomer and polymer crystals showed different fluorescence properties. All these results proved that the photo polymerization of HMTP crystals is governed by the packing structure of monomer molecules; in other words, this reaction is just lattice controlled polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1526–1534, 2005     

About crosslinking of low molecular weight ethylene‐propylene(‐diene) copolymer‐based artificial latices

Crosslinking of artificial latices based on ethylene–propylene copolymers (EPM) and/or ethylene–propylene–diene copolymers (EPDM) has not thoroughly been studied yet. Moreover, crosslinking of EPM and/or EPDM particles is a prerequisite for the formation of a shell using seeded emulsion polymerization of, for example, methyl methacrylate (MMA), as described elsewhere. Therefore, the aim of this article is to improve the general understanding of the chemistry involved in the crosslinking process. This work especially emphasizes the influence of the initiation method, that is, a peroxide or a pulsed electron‐beam, on crosslinking efficiency. All crosslinking efficiencies were obtained after extraction of the soluble polymer by tetrahydrofuran. The incorporation of the coagent, that is, divinylbenzene, into the EPM/EPDM phase was studied on a microscopic level by solid‐state ¹³C and ¹H nuclear magnetic resonance (NMR). Crosslinking of a low molecular weight EPM/EPDM latex requires the presence of a coagent, for example, divinylbenzene, 1,6‐hexanediol diacrylate, or poly(1,2‐butadiene). The efficiency of crosslinking initiated by a pulsed electron‐beam was improved to a great extent by the presence, in the aqueous phase, of potassium nitrosodisulfonate, also referred to as Fremy salt. Matrix Assisted Laser Desorption/Ionization–Time of Flight–Mass Spectrometry (MALDI‐TOF‐MS) was used to determine the influence of electron‐beam irradiation on the chemical stability of surfactants. It was demonstrated that sodium dodecyl benzene sulfonate (SDBS) is not degraded by the irradiation, and is therefore the surfactant of choice for the stabilization of EPM/EPDM‐based latices subjected to electron‐beam irradiation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3600–3615, 2005     

Synthesis and polymerization of amphiphilic methacrylates containing permanent dipole azobenzene chromophores

New amphiphilic photochromic methacrylates with the structures of 4‐[ω‐methacryloyloxyoligo(ethyleneglycol)]‐4′‐cyanoazobenzene (MEn) and 4‐methacryloyloxy‐4′‐{2‐cyano‐3‐oxy‐3‐[ω‐methoxyoligo(ethyleneglycol)]prop‐1‐en‐1‐yl}azobenzene (MEnMe) and oligo(oxyethylene) segments of different lengths were synthesized. These methacrylates were characterized by the presence of permanent dipole azobenzene chromophores and hydrophilic oligo (oxyethylene) segments. The methacrylates were obtained with six‐step and five‐step synthetic sequences, respectively, in 12–47% overall yields. The radical polymerization of the MEn monomers afforded a 50% yield of the corresponding polymers as orange solids with a number‐average molecular weight of about 40 kD. No solid polymer was obtained from the radical polymerization of the MEnME compounds. Two‐dimensional NMR spectra allowed the unequivocal assignment of the NMR signals and demonstrated a significant contribution of internal charge transfer to the electronic distribution of the azobenzene chromophore. Relaxation time measurements confirmed that the flexible polyether segment effectively decoupled photochromic groups from the polymer backbone. Optical microscopy, differential scanning calorimetry analysis, and X‐ray diffraction data demonstrated the presence of interdigitated smectic mesophases. The stability of mesophases showed a significant dependence on the chemical structure of the analyzed compounds. The glass‐transition temperatures of the polymers were rather low because of the plasticizing effect of the spacers. The monomers and polymers were used for the deposition of Langmuir films and Langmuir–Blodgett–Kuhn multilayers. A strong influence of the macromolecular structure on the film properties was observed. The photoresponsive properties of monomers and polymers were investigated with irradiation at different wavelengths. Isomerization kinetics were independent of both molecular weight and spacer length. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2957–2977, 2001     

Phase morphology and rheological properties of metallocene‐catalyzed linear low‐density polyethylene with a small amount of diatomite/oligomer hybrids

The effects of diatomite/oligomers hybrids on the phase morphology and rheology of metallocene‐catalyzed linear low‐density polyethylene (mLLDPE) were investigated. The interfacial tension between the components of the mLLDPE/hybrids influenced the dispersion of the filler and oligomer in the matrix and thus the ultimate rheological properties. Polyethylene wax (PEW) oligomer had good compatibility with the mLLDPE matrix. When a diatomite/PEW hybrid (HD‐b) was added, PEW and diatomite were dispersed separately in the mLLDPE matrix. PEW acted as a plasticizer whereas diatomite acted as a filler in mLLDPE/HD‐b. No synergetic effect was observed for HD‐b on the viscosity reduction of mLLDPE. Poly(ethylene glycol) (PEG) oligomer was incompatible with mLLDPE but had good affinity to diatomite particles. With the addition of a diatomite/PEG hybrid, a special phase morphology with an encapsulation structure with a rigid core of diatomite and a shell of PEG lubricant formed. This special phase morphology reduced the viscosity of mLLDPE significantly; that is, the addition of diatomite/PEG had a synergetic effect on the viscosity reduction of mLLDPE in comparison with the addition of PEG alone. The effect of the interfacial tension between the components of the mLLDPE/hybrid system on the rheological properties of mLLDPE was investigated. For hybrids to exhibit a synergetic effect on the viscosity reduction of the polymer matrix, they needed to fulfill the following conditions: (1) the fillers had to have good affinity to the oligomer and (2) the oligomer had to be incompatible with the polymer matrix. According to the principles, diatomite was blended with oxidized polyethylene wax (OPEW). This proved that the diatomite/OPEW hybrid exhibited a synergetic effect on the viscosity reduction of polyoxymethylene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1287–1295, 2006     

Synthesis of photocrosslinkable hyperbranched polyesters and their film properties

Hyperbranched polyesters with terminal methacryloyl groups (HBPEAc) were synthesized by the one‐pot polyaddition of bisphenol A diglycidyl ether and trimesic acid in the presence of methacrylic acid with a number‐average molecular weights of 5100–7700 in 70–83% yields. The photoradical polymerization of HBPEAc was examined in the presence of 2‐methyl‐1‐[4‐(methylthio)phenyl]‐2‐morpholinopropan‐2‐one (Irgacure 907®) as a photoinitiator in the film state upon UV irradiation to afford the corresponding cured films quantitatively. The crosslinking densities of the cured films of HBPEAc were higher than those of the corresponding linear ones, and birefringence cannot be detected for the cured films of HBPEAc because of their random structures. Furthermore, an alkaline‐developable hyperbranched polyester containing pendant carboxyl groups (HBPEAc‐COOH) was prepared by the addition reaction of HBPEAc with cis‐1,2,3,6‐tetrahydrophthalic anhydride, and its patterning properties were examined to give the resolution of a 55‐μm‐line and 275‐μm‐space pattern by UV irradiation with 700 mJ/cm². © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4642–4653, 2005     

Oligoethylene‐end‐capped polylactides

Oligoethylene‐end‐capped polylactides were synthesized through the ring‐opening polymerization of L ‐lactide with alcohol‐terminated oligoethylenes as macroinitiators. The polymerization of L ‐lactide was carried out in bulk at 130 °C in the presence of stannous octoate and primary alcohols with four different molecular weights: 350, 425, 550, and 700 g/mol. The end‐capped copolymers that formed had a number‐average molecular weight of approximately 40,000 (weight‐average molecular weight/number‐average molecular weight = 1.7) according to gel permeation chromatography and were highly crystalline in comparison with the similarly formed homopolymer of L ‐lactide. The copolymer structure was characterized by Fourier transform infrared, NMR, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, and differential scanning calorimetry analysis. This work focused on developing more crystallizable and hydrolytically stable polylactide derivatives that could potentially be used as compatibilizers in polylactide–polyolefin blends or as nucleating agents for poly(L ‐lactide) or other polyesters. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5257–5266, 2005     

Polymer characterization by interaction chromatography

Liquid chromatography (LC) is a powerful tool for the characterization of synthetic polymers, that are inherently heterogeneous in molecular weight, chain architecture, chemical composition, and microstructure. Of different versions of the LC methods, size exclusion chromatography (SEC) is most commonly used for the molecular weight distribution analysis. SEC separates the polymer molecules according to the size of a polymer chain, a well‐defined function of molecular weight for linear homopolymers. The same, however, cannot be said of nonlinear polymers or copolymers. Hence, SEC is ill suited for and inefficient in separating the molecules in terms of chemical heterogeneity, such as differences in chemical composition of copolymers, tacticity, and functionality. For these purposes, another chromatographic method called interaction chromatography (IC) is found as a better tool because its separation mechanism is sensitive to the chemical nature of the molecules. The IC separation utilizes the enthalpic interactions to vary adsorption or partition of solute molecules to the stationary phase. Thus, it is used to separate polymers in terms of their chemical composition distribution or functionality. Further, the IC method has been shown to give rise to much higher resolution over SEC in separating polymers by molecular weight. We present here our recent progress in polymer characterization with this method. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1591‐1607, 2005     

Exploration of high‐resolution ultrasonic spectroscopy as an analytical tool to study demixing and remixing in poly(N‐isopropyl acrylamide)/water solutions

The ultrasonic properties of poly(N‐isopropyl acrylamide) (PNIPAM)/water solutions, determined with high‐resolution ultrasonic spectroscopy (HR‐US), change during demixing and remixing. All HR‐US measurements are discussed with respect to modulated temperature differential scanning calorimetry results. The lower critical solution temperature type of phase behavior, in combination with the glass‐transition/composition curve of PNIPAM/water, determines the evolution of the ultrasonic signals. Three different temperature regions can be distinguished: a homogeneous region and a heterogeneous region, the latter subdivided into zones without and with interference of partial vitrification of the PNIPAM‐rich phase. During phase separation, the ultrasonic velocity decreases because of a change in the hydration structure around the polymer chains, whereas the ultrasonic attenuation increases as aggregation sets in. Isothermal measurements clearly show time dependence for both the velocity and the attenuation. The observed timescales are different and can be related to a changing polymer/water interphase and aggregate formation, respectively. Partial vitrification of the PNIPAM‐rich phase slows the demixing kinetics and especially the remixing kinetics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1283–1295, 2005     

Copolyimide imidization induced by far‐infrared radiation

The copolyimides derived from 3,4′‐oxidianiline (ODA), 4,4′‐oxydiphthalic anhydride (ODPA) and 3,3′,4,4′‐biphenyl dianhydride (BPDA) were synthesized in N,N‐dimethyl acetamide (DMAc) by a two‐step method. To control molecular weight, phthalic anhydride (PA) was used as an end‐capping reagent. The effect of far‐infrared radiation (FIR) on imidization of copolyimides was investigated by Fourier transform infrared spectroscopy (FT‐IR) and Thermogravimetric analysis (TGA), and was compared to conventional electrothermal imidization. The effect of imidization time and film thickness on weight loss of imidization process was also studied. The results show that the FIR can accelerate the imidization process of copolyimides compared with the conventional electrothermal treatment especially during the primary curing period. Weight loss of thin film is faster than that of thick film. In addition, molecular weight will influence the imidization process. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2154–2160, 2005     

Radical polymeric photoinitiators bearing side‐chain camphorquinone moieties linked to the main chain through a flexible spacer

New polymeric photoinitiators bearing the side‐chain camphorquinone moiety spaced from the backbone by a long and flexible connection have been prepared and tested in the photocuring of acrylic monomers upon irradation with visible light in the presence of tertiary amine coinitiator. The results indicate that the photoinitiating activity of the polymeric initiators may be comparable to the related combination of low molecular weight derivatives when the camphorquinone component has a polymeric structure, and depends on the chemical structure of both the components of the initiator/coinitiator pair. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5879–5888, 2005     

Structure–property relationship in high urethane density polyurethanes

The structure–property relationship of polyurethane (PU) homopolymers synthesized by the stoichiometric combination of 1,6‐hexamethylene diisocyanate (HDI) and low‐molecular‐weight glycols with different structure is investigated by the analysis of PU elastic modulus obtained by means of high‐resolution peak force atomic force microscopy. Different experimental techniques are employed to understand the role of block structure influence on hydrogen bonding distribution, crystallinity, thermal transitions, and crystal packaging within the PU. The results show that glycols with bulky side groups have more impediments to self‐assemble into hydrogen‐bonded and packed macromolecular structures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 739–746     

New selenium‐based iniferter agent for living free radical polymerization of styrene under UV irradiation

P,P‐Diphenyl phosphinodiselenoic acid benzyl ester was synthesized and used as a mediator for the polymerization of styrene under UV–vis irradiation. Moderately controlled evidence was found: linear polymerization kinetics, linear evolution of molecular weight with monomer conversion, and relatively narrow molecular weight distribution (1.5–2.0). The structure of the obtained polymers was characterized using NMR and oxidative eliminaton. Based on polymerization results, an iniferter mechanism was proposed for the current polymerization system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012