Isotactic Poly(propylene)/Monoalkylimidazolium‐Modified Montmorillonite Nanocomposites: Preparation by Intercalative Polymerization and Thermal Stability Study

Summary: Poly(propylene)/monoalkylimidazolium‐modified montmorillonite (PP/IMMT) nanocomposites were prepared by in situ intercalative polymerization of propylene with TiCl₄/MgCl₂/MMT catalyst. The PP synthesized possessed high isotacticity and molecular weight. Both wide‐angle X‐ray diffraction (XRD) and transmission electron microscopy (TEM) examinations evidenced the nanocomposite formation with exfoliated MMT homogeneously distributed in the PP matrix. A thermal stability study revealed that the nanocomposites possess good thermal stability.

X‐ray diffraction patterns of PP/IMMT (MMT = 2.2 wt.‐%) nanocomposite before and after processing.     

Free Volume of Montmorillonite/Styrene‐Butadiene Rubber Nanocomposites Estimated by Positron Annihilation Lifetime Spectroscopy

Summary: The size and concentration of free‐volume holes of two kinds of montmorillonite (MMT)/styrene‐butadiene rubber (SBR) nanocomposites were investigated by positron annihilation lifetime spectroscopy (PALS). Strong interfacial interaction caused an apparent reduction of the free‐volume fraction of rubber probably by depressing the formation of free‐volume holes in the interfacial region. Interfacial interaction in MMT/SBR nanocomposites was weaker than that in SBR filled with carbon black.

Dependence of normalized o‐Ps intensity of four kinds of composites on filler volume fraction.     

Nanocomposites of poly(ethylene terephthalate‐co‐ethylene naphthalate) with organoclay

Poly(ethylene terephthalate‐co‐ethylene naphthalate) (PETN)/organoclay was synthesized with the solution intercalation method. Hexadecylamine was used as an organophilic alkylamine in organoclay. Our aim was to clarify the intercalation of PETN chains to hexadecylamine–montmorillonite (C₁₆–MMT) and to improve both the thermal stability and tensile property. We found that the addition of only a small amount of organoclay was enough to improve the thermal stabilities and mechanical properties of PETN/C₁₆–MMT hybrid films. Maximum enhancement in both the ultimate tensile strength and initial modulus for the hybrids was observed in blends containing 4 wt % C₁₆–MMT. Below a 4 wt % clay loading, the clay particles could be highly dispersed in the polymer matrix without a large agglomeration of particles. However, an agglomerated structure did form in the polymer matrix at a 6 wt % clay content. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2581–2588, 2001     

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     

Blends of a thermotropic liquid‐crystalline polymer and a poly(butylene terephthalate)/organoclay nanocomposite

Blends were synthesized via the melt blending of a thermotropic liquid‐crystalline polymer (TLCP) and a poly(butylene terephthalate) (PBT) hybrid containing 2 wt % organoclay. A TLCP was also synthesized with side groups based on a nematic liquid‐crystalline phase. The blends of TLCPs with PBT hybrids were melt‐spun with different concentrations of the liquid‐crystalline polymer and different draw ratios (DRs) to produce monofilaments. Regardless of the TLCP concentration in the hybrids, transmission electron microscopy photographs proved that the clay layers of the organoclay were intercalated and partially exfoliated in the PBT matrix. At DR = 1, the maximum enhancement in the ultimate tensile strength was observed for blends containing 8% TLCP, and the tensile strength decreased with further increases in the TLCP concentration. The initial modulus monotonically increased with increasing TLCP concentration. When DR increased from 1 to 44, the increased stretching caused the tensile property to decrease significantly, debonding to occur, and voids to form. These trends with increasing DR were observed in all the systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3667–3676, 2004     

High‐Performance Exfoliated Poly(propylene)/Clay Nanocomposites by In Situ Polymerization with a Novel Z–N/Clay Compound Catalyst

Highly exfoliated poly(propylene) (PP)/clay nanocomposites with obvious improvements in both the tensile strength and toughness have been prepared by a novel TiCl₄/MgCl₂/imidazolium‐modified montmorillonite (IOHMMT) compound catalysts. Through this approach, in situ propylene polymerization can actually take place between the silicate layers and lead not only to PP with a high isotacticity and molecular weight, but also to a highly exfoliated structure even at high clay content levels (as high as 19 wt.‐%).

     

Acrylonitrile‐Butadiene Rubber (NBR) Prepared via Living/Controlled Radical Polymerization (RAFT)

In the current work we present results on the controlled/living radical copolymerization of acrylonitrile (AN) and 1,3‐butadiene (BD) via reversible addition fragmentation chain transfer (RAFT) polymerization techniques. For the first time, a solution polymerization process for the synthesis of nitrile butadiene rubber (NBR) via the use of dithioacetate and trithiocarbonate RAFT agents is described. It is demonstrated that the number average molar mass, , of the NBR can be varied between a few thousand and 60 000 g · mol⁻¹ with polydispersities between 1.2 and 2.0 (depending on the monomer to polymer conversion). Excellent agreement between the experimentally observed and the theoretically expected molar masses is found. Detailed information on the structure of the synthesized polymers is obtained by variable analytical techniques such as infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry, and electrospray ionization‐mass spectrometry (ESI‐MS).

     

Microstructure and relaxation behavior of flexible dielectric PVDF and HNBR blends: An assessment through small‐angle x‐ray scattering and dielectric relaxation spectroscopy

The work demonstrated the microstructure and the relaxation behavior of flexible electroactive blends of poly(vinylidene fluoride) (PVDF)/hydrogenated nitrile rubber (HNBR) by small‐angle X‐ray scattering and dielectric relaxation spectroscopy. Very few studies have been done so far on this topic for crystalline/rubbery blends. Lamellar morphology was observed for both the PVDF and its blends. HNBR suppressed the mobility of PVDF above its melting temperature, as evident from lowering of crystallization temperature, due to physical interaction. The interaction was increased with HNBR content. However, after complete crystallization, HNBR segments were expelled out from the lamella, and crystal long period remained intact in all the blends. Interestingly, some HNBR segments remained in the amorphous part of PVDF which reduced the electron density contrast of its crystalline and amorphous region. When HNBR was crosslinked, the interaction was reduced, and consequently, the crystallization became faster and electron density contrast increased. From the microscopic study, polydispersed particles were observed within the crystalline lamella. Interfacial polarization (IP) relaxation of PVDF was absent in the blends due to physical interaction, whereas IP relaxation of HNBR shifted to a higher frequency. The shift was higher at higher HNBR content and decreased when HNBR was crosslinked. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 851–866     

Copolymerization of Ethylene and 10‐Undecen‐1‐ol using a Montmorillonite‐Intercalated Metallocene Catalyst: Synthesis of Polyethylene/Montmorillonite Nanocomposites with Enhanced Structural Stability

Summary: Ethylene and 10‐undecen‐1‐ol have been successfully copolymerized by an organically modified montmorillonite (OMMT)‐intercalated metallocene catalyst, Et[Ind]₂ZrCl₂, activated by methylaluminoxane (MAO). The obtained hydroxy‐functionalized polyethylene (PE‐OH)/OMMT nanocomposites exhibit enhanced structural stability as compared with the neat PE‐based ones, with no significant collapse of the nanocomposite structure being detected by WAXD examination after high‐temperature processing. The simultaneous polyolefin functionalization provides an effective and convenient solution to stabilize the PE/MMT nanocomposite structure formed by in‐situ polymerization.

     

Poly(butylene terephthalate)/clay nanocomposite compatibilized with poly(ethylene‐co‐glycidyl methacrylate). II. Nonisothermal crystallization

Melting behaviors and nonisothermal crystallization of poly(butylene terephthalate)/poly(ethylene‐co‐glycidyl methacrylate) (PBT/PEGMA), PBT/commercial modified montmorillonite clays (PBT/Clay), and PBT/exfoliated silicates (PBT/PEGMA/Clay) nanocomposites were studied by wide‐angle X‐ray diffraction and differential scanning calorimeter. PEGMA is used as a compatibilizer. For both isothermally and nonisothermally crystallized samples, PEGMA facilitates the recrystallization of PBT during the heating scans, and leads to a less degree of perfection of the crystals. However, the clay hinders the recrystallization growth during heating scans, and increases perfection of the crystals. Nonisothermal crystallization kinetics was described by kinetic models and undercooling was taken into account. The PEGMA would lead to an increase of the blend viscosity, rendering the chains less mobile and lower the crystallizability of PBT in PBT/PEGMA. The well‐dispersed exfoliated silicates in PBT/PEGMA/Clay cause a large number of nuclei to precede crystallization. The fold surface free energy (σ_e) and activation energy also supported the interpretation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 564–576, 2008     

Poly(styrene‐b‐tetrahydrofuran)/clay nanocomposites by mechanistic transformation

Synthesis of poly(styrene‐block‐tetrahydrofuran) (PSt‐b‐PTHF) block copolymer on the surfaces of intercalated and exfoliated silicate (clay) layers by mechanistic transformation was described. First, the polystyrene/montmorillonite (PSt/MMT) nanocomposite was synthesized by in situ atom transfer radical polymerization (ATRP) from initiator moieties immobilized within the silicate galleries of the clay particles. Transmission electron microscopy (TEM) analysis showed the existence of both intercalated and exfoliated structures in the nanocomposite. Then, the PSt‐b‐PTHF/MMT nanocomposite was prepared by mechanistic transformation from ATRP to cationic ring opening polymerization (CROP). The TGA thermogram of the PSt‐b‐PTHF/MMT nanocomposite has two decomposition stages corresponding to PTHF and PSt segments. All nanocomposites exhibit enhanced thermal stabilities compared with the virgin polymer segments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2190–2197, 2009     

Tailor‐made hybrid nanostructure of poly(ethyl acrylate)/clay by surface‐initiated atom transfer radical polymerization

Hybrid nanoarchitecture of tailor‐made Poly(ethyl acrylate)/clay was prepared by surface‐initiated atom transfer radical polymerization (SI‐ATRP), by tethering ATRP initiator on active hydroxyl group, present in surface as well as in the organic modifier of the clay used. Extensive exfoliation was facilitated by using these initiator modified clay platelets. Poly(ethyl acrylate) chains with controlled polymerization and narrow polydispersities were forced to be grown from within the clay gallery (intergallery) as well as from the outer surface (extragallery) of the clay platelets. The polymer chains attached onto clay surfaces might have the potential to provide the composites with enhanced compatibility in blends with common polymers. Attachment of the initiator on clay platelets was confirmed by Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), elemental analysis, Wide‐angle X‐ray diffraction (WAXD), and microscopic analysis. Finally, end group analysis (by Matrix‐Assisted Laser Desorption Ionization Mass Spectrometry, and chain extension experiment) of the cleaved polymer and morphological study (by WAXD, Transmission Electron Microscopy), performed on the polymer grafted clays examined the effect of grafting on the efficiency of polymerization and the degree of dispersion of clay tactoids in polymer. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5014–5027, 2008     

A novel sodium carboxymethylcellulose/poly(N‐isopropylacrylamide)/Clay semi‐IPN nanocomposite hydrogel with improved response rate and mechanical properties

A novel semi‐IPN nanocomposite hydrogel (CMC/PNIPA/Clay hydrogel) based on linear sodium carboxymethylcellulose (CMC) and poly(N‐isopropylacrylamide) (PNIPA) crosslinked by inorganic clay was prepared. The structure and morphology of these hydrogels were investigated and their swelling and deswelling kinetics were studied in detail. TEM images showed that the clay was substantially exfoliated to form nano‐dimension platelets dispersed homogeneously in the hydrogels and acted as a multifunctional crosslinker. The CMC/PNIPA/Clay hydrogels swell faster than the corresponding PNIPA/Clay hydrogels at pH 7.4, whereas they swell slower than the PNIPA/Clay hydrogels at pH 1.2. The CMC/PNIPA/Clay nanocomposite hydrogels showed much higher deswelling rates, which was ascribed to more passway formed in these hydrogels for water to diffuse in and out. The deswelling process of the hydrogels could be approximately described by the first‐order kinetic equation and the deswelling rate decreased with increasing clay content. The mechanical properties of the CMC/PNIPA/Clay nanocomposite hydrogels were analyzed based on the theory of rubber elasticity. It was found that with increasing clay content, the effective crosslink chain density, v_e, increased whereas the molecular weight of the chains between crosslinks M_c decreased. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1546–1555, 2008     

Effects of clay‐modifying agents on the morphology and properties of poly(methyl methacrylate)/clay nanocomposites synthesized via γ‐ray irradiation polymerization

Via γ‐ray irradiation polymerization, poly(methyl methacrylate) (PMMA)/clay nanocomposites were successfully prepared with reactive modified clay and nonreactive clay. With reactive modified clay, exfoliated PMMA/clay nanocomposites were obtained, and with nonreactive clay, intercalated PMMA/clay nanocomposites were obtained. Both results were confirmed by X‐ray diffraction and high‐resolution transmission electron microscopy. PMMA extracted from PMMA/clay nanocomposites synthesized by γ‐ray irradiation had higher molecular weights and narrow molecular weight distributions. The enhanced thermal properties of the PMMA/clay nanocomposites were characterized by thermogravimetric analysis and differential scanning calorimetry. The improved mechanical properties of PMMA/clay were characterized by dynamic mechanical analysis. In particular, the enhancement of the thermal properties of the PMMA/clay nanocomposites with reactive modified clay was much more obvious than that of the PMMA/clay nanocomposites with nonreactive clay. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3218–3226, 2003     

Synthesis of poly(2‐ethylhexyl acrylate)/clay nanocomposite by in situ living radical polymerization

This investigation reports the preparation of tailor‐made poly(2‐ethylhexyl acrylate) (PEHA) prepared via in situ living radical polymerization in the presence of layered silicates and characterization of this polymer/clay nanocomposite. Being a low T_g (?65 °C) material, PEHA has very good film formation property for which it is used in paints, adhesives, and coating applications. 2‐Ethylhexyl acrylate was polymerized at 90 °C using CuBr and Cu(0) as catalyst in combination with N,N,N′,N″,N″‐pentamethyl diethylenetriamine (PMDETA) as ligand. A tremendous enhancement in reaction rate and polymerization data was achieved when acetone was added as additive to increase the efficiency of the catalyst system. PEHA/clay nanocomposite was prepared at 90 °C using CuBr as catalyst in combination with PMDETA as ligand. Different types of clay with same loading were also used to study the effect on reaction rate. The molecular weight (M_n) and polydispersity index of the prepared nanocomposites were characterized by size exclusion chromatography. The active end group of the polymer chain was analyzed by ¹H NMR analysis and by chain extension experiment. Polymer/clay interaction was studied by Fourier Transform Infrared spectrometry and wide‐angle X‐ray diffraction analyses. Distribution of clay in the polymer matrix was studied by the transmission electron microscopy. Thermogravimetric analysis showed that thermal stability of PEHA/clay nanocomposite increases on addition of nanoclay. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A New Approach to Prepare Poly(ethylene terephthalate)/Silica Nanocomposites with Increased Molecular Weight and Fully Adjustable Branching or Crosslinking by SSP

Summary: In the present study, it has been unexpectedly found that solid‐state polycondensation (SSP) can act as a facile method to prepare poly(ethylene terephthalate)/silica (PET/SiO₂) nanocomposites with high molecular weight and an adjustable degree of branching or crosslinking. Fumed silica, with its surface silanol groups, seems to participate in some kind of reaction, probably esterification with the hydroxy end‐groups of PET, during SSP, to act as a multifunctional chain extender. Differential scanning calorimetry and FT‐IR spectroscopy reveal this ability of the silanol groups. The molecular weight increase depends on the used temperatures of SSP as well as on the amount of SiO₂ added. As the amount of silica increases the rate of increase of the intrinsic viscosity slows because of the higher extent of branching. At 5 wt.‐% SiO₂ the extensive branching produces a crosslinked polymeric material. Such polyesters with increased molecular weight and low silica content could be suitable for blown bottle production, while the high SiO₂ content and adjustable branching or crosslinking could make them ideal high‐melt‐strength resins suitable for the preparation of low‐density closed‐shell foams.

Schematic representation of PET/SiO₂ crosslinked macromolecules.     

Suitability of Stripping Chronopotentiometry for Heavy Metal Speciation Using Hydrogen Peroxide as Oxidant: Application to the Cd(II)‐EDTA‐PMA System

The possibilities of stripping chronopotentiometry (SCP) for heavy metal speciation have been tested in the modality of chemical oxidation using the model systems Cd(II)‐polyacrylic acid (PMA), Cd(II)‐EDTA and Cd(II)‐PMA‐EDTA. The use of 0.03% H₂O₂ as a chemical oxidant provides reliable results from transition times, but peak potentials are dramatically affected by the presence of this reagent. The study suggests that chemical‐oxidation SCP can be a technique complementary to other stripping modalities in the study of inert and macromolecular labile metal complexes.     

Non‐covalent Immobilization of Iron‐triazole (Fe(Htrz)3) Molecular Mediator in Mesoporous Silica Films for the Electrochemical Detection of Hydrogen Peroxide

Mesoporous silica thin films encapsulating a molecular iron‐triazole complex, Fe(Htrz)₃ (Htrz=1,2,4,‐1H‐triazole), have been generated by electrochemically assisted self‐assembly (EASA) on indium‐tin oxide (ITO) electrode. The obtained modified electrodes are characterized by well‐defined voltammetric signals corresponding to the Fe^II/III centers of the Fe(Htrz)₃ species immobilized into the films, indicating fast electron transfer processes and stable operational stability. This is due to the presence of a high density of redox probes in the material (1.6×10^?4 mol g^?1 Fe(Htrz)₃ in the mesoporous silica film) enabling efficient charge transport by electron hopping. The mesoporous films are uniformly deposited over the whole electrode surface and they are characterized by a thickness of 110 nm and a wormlike mesostructure directed by the template role played by Fe(Htrz)₃ species in the EASA process. These species are durably immobilized in the material (they are not removed by solvent extraction). The composite mesoporous material (denoted Fe(Htrz)₃@SiO₂) is then used for the electrocatalytic detection of hydrogen peroxide, which can be performed by amperometry at an applied potential of ?0.4 V versus Ag/AgCl and by flow injection analysis. The organic‐inorganic hybrid film electrode displays good sensitivity for H₂O₂ sensing over a dynamic range from 5 to 300 μM, with a detection limit estimated at 2 μM.     

Electrocatalytic Oxidation of Hydrogen Peroxide on Poly(m‐toluidine)‐Nickel Modified Carbon Paste Electrode in Alkaline Medium

The poly(m‐toluidine) film was prepared by using the repeated potential cycling technique in an acidic solution at the surface of carbon paste electrode. Then transition metal ions of Ni(II) were incorporated to the polymer by immersion of the modified electrode in a 0.2 M NiSO₄, also the electrochemical characterization of this modified electrode exhibits stable redox behavior of the Ni(III)/Ni(II) couple. The electrocatalytic ability of Ni(II)/poly(m‐toluidine)/modified carbon paste electrode (Ni/PMT/MCPE) was demonstrated by electrocatalytic oxidation of hydrogen peroxide with cyclic voltammetry and chronoamperometry methods in the alkaline solution. The effects of scan rate and hydrogen peroxide concentration on the anodic peak height of hydrogen peroxide oxidation were also investigated. The catalytic oxidation peak current showed two linear ranges with different slopes dependent on the hydrogen peroxide concentration and the lower detection limit was 6.5 μM (S/N=3). The catalytic reaction rate constant, (k_h), was calculated 5.5×10² M^?1 s^?1 by the data of chronoamperometry. This modified electrode has many advantages such as simple preparation procedure, good reproducibility and high catalytic activity toward the hydrogen peroxide oxidation. This method was also applied as a simple method for routine control and can be employed directly without any pretreatment or separation for analysis cosmetics products.     

A non‐PFT (polymerization filling technique) approach to poly(ethylene‐co‐norbornene)/MWNTs nanocomposites by in situ copolymerization with scandium half‐sandwich catalyst

The in situ synthesis of ethylene‐co‐norbornene copolymers/multi‐walled carbon nanotubes (MWNTs) nanocomposites was achieved by rare‐earth half‐sandwich scandium precursor [Sc(η⁵‐C₅Me₄SiMe₃)(η¹‐CH₂SiMe₃)₂(THF)] (1) activated by [Ph₃C][B(C₆F₅)₄], through a non‐PFT (Polymerization Filling Technique) approach. MWNTs nanocomposites with low aluminum residue were obtained with excellent yields even though small amounts of triisobutylaluminium were needed as scavenger to prevent catalyst poisoning by MWNT impurities. MWNT bundles were disaggregated and highly coated with Poly(ethylene‐co‐norbornene) [P(E‐co‐N)] as revealed by transmission electron microscopy. Interestingly, P(E‐co‐N) copolymers showed T_g over 130 °C as well as norbornene content over 50 mol %; both values were higher than those obtained by the cationic active species in 1 /[Ph₃C][B(C₆F₅)₄]. A series of copolymerization reactions by 1 /[Ph₃C][B(C₆F₅)₄]/AlⁱBu₃ without MWNTs produced copolymers with the same unexpected features. The NMR analysis revealed the presence of rac‐ENNE and rac‐ENNNE sequences. Thus, AlⁱBu₃ changed the stereoirregular alternating copolymer microstructure produced by 1 /[Ph₃C][B(C₆F₅)₄]. We conclude that AlⁱBu₃ is not only a scavenger for CNT impurities, but it reacts with the THF ligand to give coordinatively unsaturated active species. Finally, P(E‐co‐N)/MWNT masterbatches were mixed with commercial TOPAS to produce cyclic olefin copolymer nanocomposites with excellent dispersion of filler. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5709–5719, 2009