Investigation of 1,3,5-tris(2-metoxypropane)benzene/BCl3 initiated living isobutylene polymerization by C13 and B11 NMR spectroscopy

Summary The living carbocationic polymerization of isobutylene initiated by 1,3,5-tris(2-methoxypropane) benzene (TriCumOMe)/BCl₃ system was investigated by C¹³ and B¹¹ NMR spectroscopy. The reaction between the TriCumOMe and BCl₃ at-30°C in CH₂Cl₂ after 15 mins reaction time resulted in 1,3,5-tris(2-chloropropane) benzene (TriCumCl) and methyl-dichloroboronite (BCl₂OMe). The same system in the presence of isobutylene yielded three-arm star, chlorine terminated telechelic polyisobutylene and BCl₂OMe. No counterions, i.e., BCl₃OMe, BCl ₄ , or neutral boron complexes, e.g., TriCumOMe, 3BCl₃ could be detected. The simultaneous measurement of static permittivity (direct monitoring method) showed different reaction rate patterns in the case of AMI method, and when the TriCumOMe+BCl₃ mixture was aged and the polymerization was started by isobutylene.     

Investigation of the mechanism of living cationic polymerization of isobutylene by B11 NMR spectroscopy

Summary The living carbocationic polymerization of isobutylene initiated by tri-cumyl-ether (1)/BCl₃ and tricumyl-acetate(2)/BCl₃ was investigated by B¹¹ NMR spectroscopy in the presence and absence of DMSO. With BCl₃, 1 yields tri-cumyl-chloride and BCl₂OMe due to fast exchange reaction, while 2 forms complexes. If the 1/BCl₃ mixture contains DMSO, well defined complexes can be detected, i.e., DMSO.BCl₃ and BCl₂OMe.DMSO. In the system 2/BCl₃/DMSO neutral complexes with broad NMR signals are formed. In the presence of isobutylene (real polymerization mixture) the same complexes can be detected.     

Living polymerization of isobutylene initiated byp-dicumyl chloride/BCl3/n-Bu4NX systems

Summary The 1,4-di-(2-chloro-2-propyl)-benzene (pDCC)/BCl₃/IB system was investigated in the presence and absence ofn-Bu₄NX. The presence ofn-Bu₄NX (X=Cl or I) changes the mechanism increasing the living character of the polymerization of isobutylene in both cases. Whenn-Bu₄NCl is added, BCl₄ ^– is formed and as a common ion in excess it shifts the dissociation equilibrium toward the non-dissociated species. In the case of the addition ofn-Bu₄NI, an exchange reaction between the gegenions, i.e., BCl₄ ^– and BCl₃I^– has been recognised and a possible reaction mechanism is given.     

Dielectric properties of Sr0.5Ca0.5TiO3: x Pr3+ ceramics

The frequency dependent dielectric and AC conductivity properties of different concentrations of Pr³⁺ doped Sr_0.5Ca_0.5TiO₃ ceramics were investigated for the frequency range 100 Hz to 2 MHz at different temperatures. The morphology of the prepared samples was analyzed by using Field-Emission Scanning Electron Microscope images. The value of dielectric constant and dielectric loss decreases with increase in the frequency of the applied signal in all the samples. Also, the value of dielectric constant and dielectric loss decreased with doping of different concentrations of Pr³⁺ ions. The conductivity of the samples obeys Jonscher's power-law and shows a decrease with increasing doping concentration of Pr³⁺ ions. The higher value of real and imaginary part of impedance at lower frequency indicates the space charge polarization of the material and its absence at higher frequencies was confirmed from the low value of impedance at higher frequency region. The Cole- Cole parameters of the samples were calculated and the semi-circle observed indicates a single relaxation process and can be modeled by an equivalent parallel RC circuit. At lower frequency region, the value of dielectric constant and dissipation factor increases with increase in the temperature. Also the value of conductivity increases with temperature at high frequency region, due to the enhanced mobility of charge carriers.     

Free radical copolymerization behavior of vinyl acetate with butyl acrylate in the presence of GeCl4 and BCl3

No alternating copolymers of vinyl acetate (VAc) and butyl acrylate (BA) were obtained by free radical copolymerization in the presence of GeCl₄ and BCl₃ (compared with the acrylic acid–vinyl acetate copolymerization system). By ultraviolet spectral analysis, it was concluded that both BCl₃ and GeCl₄ can form complexes with butyl acrylate. The BA–BCl₃ complex constants were determined by ¹H NMR; K_B=33·2 (25°C). The reason for the gel formation in the BA–Vac–BCl₃ copolymerization system was discussed. When vinyl acetate reacted with BCl₃, cationic polymerization probably occurred. A white gel product probably resulted from the polymerization of the BA–BCl₃ complex. © 1998 SCI.     

Frequency, temperature and In dependent electrical conduction in NiFe2O4 powder

A series of polycrystalline spinel ferrites with the composition NiIn_xFe_2-xO₄ (0 ≤ x ≤ 0.3) were prepared by the solid state reaction to study the effect of In³⁺ ions substitution on their dc electrical resistivity and dielectric properties. The dc resistivity has been investigated as a function of temperature and composition. The indium ion increases the dc resistivity and activation energy of the system. A study of the dielectric properties of these mixed ferrites, as a function of composition, frequency and temperature, has been undertaken. The dielectric constant (ε′), dielectric loss (ε″) and dielectric loss tangent (tanδ) all decreases with frequency as well as with the composition. The dielectric constant (ε′) and dielectric loss tangent (tanδ) were increases with increasing temperature. AC conductivity increases with increase in applied frequency. The dielectric behavior of the present samples is attributed to the Maxwell-Wagner type interfacial polarization. The conduction mechanism in these ferrites is due to electron hopping between Fe²⁺ and Fe³⁺ ions on adjacent octahedral sites.     

Ba and Mg co-doping to suppress high-temperature dielectric loss in lead-free Na0.5Bi0.5TiO3-based systems

In this study, Ba, Mg co-doped BNT-based ferroelectric ceramic (Ba_0.2Na_0.3Bi_0.5)Ti_0.9Mg_0.1O₃ is fabricated by conventional solid-state reaction to obtain high-temperature dielectric performance. The temperature dependent dielectric constant and dielectric loss are investigated to understand the high-temperature dielectric behavior of the ceramic. The results show that Ba, Mg co-doped BNT ceramic has a very low dielectric loss (about 0.006–0.023) in a wide temperature range of 200–400 °C with dielectric constant about 3200–3800. The complex impedance plots, temperature dependent conductivity and first principle results reveal that the low dielectric loss at high-temperature is mainly due to the Ba doping increases the migration barrier energy of oxygen ions in BNT. The oxygen ion conduction of BNT-based ceramics is restrained, so that the dielectric loss reduces significantly. The study provides a new BNT-based material with low dielectric loss and temperature- stable dielectric constant in a wide temperature range which has great value of high-temperature applications.     

Tailoring the structural,magnetic and dielectric properties of Ni-Zn-CdFe2O4 spinel ferrites by the substitution of lanthanum ions

In this paper, we have tailored the structural, magnetic and dielectric properties of Ni_0.5Zn_0.3Cd_0.2Fe_2-yLa_yO₄ (y?=?0.0–0.21) nano-structured spinel ferrites by the substitution of La³⁺ ions. The investigated samples were synthesized by Sol-gel auto-combustion method and were characterized using XRD, SEM, VSM, FTIR and dielectric measurements. Single phase nanostructure formation of synthesized material was confirmed by XRD analysis. The effect of La³⁺ ions on crystallite size, grain size, lattice constant and bulk densities was calculated and it was found that lattice constant first increased upto concentration y?=?0.105 then decreased with further substitution of dopant ions. FTIR results for all synthesized samples demonstrated two absorption bands at υ₁ =?540.8?cm^?1 and υ₂ =?490.8?cm^?1 corresponds to tetrahedral and octahedral sites of spinel structure respectively. With the increase in La³⁺ ions concentration, saturation magnetization and remanence both found to be decreased down to lowest M_s value of 34.1?emu/g which is not yet reported in the literature according to best of our knowledge. Dielectric results showed that by decreasing frequency, both dielectric loss and dielectric constant decreases. AC conductivity has two regions, at low frequency region ac conductivity increases while at high frequency region, it decreases with increasing frequency. The measured results for all synthesized nano-ferrites suggested that synthesized nanoferrites are recommended for high frequency and microwave absorbing applications.     

Synthesis and characterization of PPY/K[Fe(CN)3(OH)(en)] nanocomposite: Study of photocatalytic,sorption, electrical,and thermal properties

This work involves the synthesis of nanocomposite of Polypyrrole (PPY) with photoadduct {K[Fe(CN)₃(OH)(en)]} via in‐situ oxidative chemical polymerisation. Photoadduct is synthesized by irradiating equimolar mixture of potassium hexacyanoferrate (III) and ethylenediamine (en) and is then reduced to nanosize by high energy ball mill. Successful synthesis of nanophotoadduct is confirmed by elemental analyser, UV–Vis, and FTIR. The nanocomposite of PPY and photoadduct has been characterised by SEM, TEM, FTIR, XRD, TGA, UV–Vis spectroscopy, I–V characteristics, and dielectric analysis for structural, thermal, optical, electrical, and dielectric properties. The average particle size of nanophotoadduct and nanocomposite has been found to be 80 and 84 nm, respectively. The thermal stability of nanocomposite is enhanced. The nanocomposite shows high value of dielectric constant (5 × 10³ at10³ Hz) and ac conductivity (7.0 × 10⁸ Sm^?1 at 10⁶ Hz) as compared with pure PPY. The high value of dielectric constant can make the material suited for energy storage applications. The nanocomposite shows higher photocatalytic activity as compared with pure PPY and a high value of distribution coefficient (K_d) has been obtained for Pb²⁺, Zn²⁺, and Cd²⁺ ions, hence, can act as an efficient material for removal of dyes and heavy metal ions in waste water. Thus, photoadduct of K₃[Fe(CN)₆] and ethylenediamine(en), a new kind of filler, has succeeded in improving the properties of PPY with respect to thermal stability, high dielectric constant, high ac conductivity, efficient photocatalytic activity, and high K_d value for toxic metal ions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43487.     

Living carbocationic polymerization

A new family of initiating systems has been discovered that efficiently induces the truly living polymerization of isobutylene (IB). The initiating systems are complexes of organic tertiary esters e.g., cumyl acetate, 2,4,4-trimethylpentane-2-acetate, with BCl₃. Living polymerizations proceed very rapidly in a variety of solvents, i.e., CH₃Cl, CH₂Cl₂, C₂H₅Cl, and mixtures of chlorinated solvents plus n-hexane, in the range from –10° to –50°C. The living nature of the polymerizations was demonstrated by linear ¯M_n versus W_PIB (g of polymer formed) plots starting at the origin and horizontal N (number of PIB chains) versus W_PIB plots. The DP_n of the products obeys [M_o]/[I_o] where [M_o] and [I_o] are initial monomer and initiator concentrations, respectively. Conversions and initiator efficiencies are 100%. In carefully controlled experiments narrow molecular weight distribution polyisobutylenes (PIB) have been obtained, i.e., M_w/M_n=1.17 – 1.3. A mechanism is outlined that helps rationalize the findings. It is postulated that the living polymerization of IB initiated by organic tertiary ester·BCl₃ complexes most likely proceeds by a two-component group transfer polymerization process.     

Temperature compensated microwave dielectrics based on lithium containing titanates

Ceramic materials in the system Ln_2/3−x³⁺Li_3x¹⁺TiO₃ (Ln=rare earth element), which are known to exhibit lithium ion conductivity, were examined over wide frequency and temperature ranges with regard to their conductivity (σ) and dielectric properties (ε and tg δ). In the microwave range both positive temperature coefficient of dielectric constant (τ_ε) and dielectric loss magnitude in lithium containing materials Ln_2/3−xLi_3xTiO₃ can be ascribed to the presence of lithium-ion conductivity. The substitution of rare-earth ions with smaller ionic radii for larger La ions suppresses both the cation conductivity and dielectric losses. In this case Li ions do not participate in conductivity but contribute noticeably to the relaxation. The latter results in the positive τ_ε and relatively low tg δ. Using the system Ln_2/3−xLi_3xTiO₃ as an example it has been shown that the materials with the mobile lithium cation sublattice can be used for the volume temperature compensation of microwave (MW) dielectrics with the negative τ_ε.     

Living carbocationic polymerization

Summary Living carbocationic polymerization of styrene (St) has been achieved by the use of the 1(p-methylphenyl)ethyl acetate (pMePhEtOAc)·BCl₃ complex in CH₃Cl solvent at –30°C using both the IMA and AMI techniques. The living nature of the polymerizations has been demonstrated by linear M_n versus W_PSt (weight of polystyrene) plots passing through the origin and horizontal N (moles of PSt) versus W_PSt plots starting at N=I_o (the number of moles of initiator used). The molecular weight distribution MWD of the PSts is broad (M_w/M_n=~5–6) due to slow initiation and/or slow exchange between dormant and active species relative to propagation. The structure of the ester initiator strongly affects the rate and outcome of living polymerization, e.g., cumyl acetate (CumOAc), cumyl propionate (CumOPr), and 2,4,6-trimethylphenylethyl acetate (TMePhEtOAc), do not lead to truly living St polymerizations. The findings with the latter esters is explained in terms of a two path process comprising a slow living polymerization and a faster conventional cationic chain reaction. With phenylethyl acetate (PhEtOAc) living polymerization is achieved, however, initiation (cation generation) is slow. Forced termination by pyridine or methanol, or heating to ambient temperature leads to-CH₂CH(C₆H₅)Cl end groups.     

New polyisobutylene stars XI. Synthesis and characterization of allyl-telechelic octa-arm polyisobutylene stars

The synthesis and characterization of a novel star comprising eight allyl-terminated polyisobutylene (PIB) arms radiating from a calix[8]arene core is described. The synthesis was accomplished by a core-first method, by inducing the living polymerization of isobutylene (IB) by a suitably functionalized calix[8]arene initiator (1) in conjunction with BCl₃-TiCl₄ coinitiators, and terminating the growth of the living PIB^⊕ arms by allyltrimethylsilane. The relative concentrations of BCl₃ and TiCl₄ are critical for the synthesis of well-defined 8-arm stars. Characterization of the products (which included triple detector GPC studies and ¹H NMR spectroscopy) indicated quantitative allylation. A mechanism which summarizes the experimental observations is proposed. Received: 17 July 1997/Revised version: 11 September 1997/Accepted: 19 September 1997     

Significantly high electromagnetic shielding effectiveness in polypyrrole synthesized by eco-friendly and cost-effective technique

A facile and eco-friendly synthesis of polypyrrole from monomer pyrrole using nominal amount of ferric chloride hexahydrate (FeCl₃.6H₂O) oxidant in aqueous solution by chemically oxidative polymerization method has been reported. The use of aqueous solvent and ferric chloride hexahydrate salt in polypyrrole synthesis have an eco-friendly route favorable for the production of polypyrrole in large quantities. The synthesized polypyrrole samples exhibit good electrical conductivity (2 S/cm) and yield of 80% for reaction time of 8 hr at 5°C. Quality and properties of polypyrrole samples have been thoroughly investigated with varying reaction time and temperature while other synthesis parameters like molar ratio of oxidant to monomer, oxidant concentration, and solvent were kept constant. X-ray diffraction analysis of polypyrrole with a shorter reaction time shows the presence of iron oxide (Fe₂O₃) peaks. The complete reaction may not occur at shorter reaction times due to which residual ferric ions converted into Fe₂O₃. X-ray photoelectron spectroscopy measurement of polypyrrole also confirms the formation of Fe₂O₃. Appropriate selection of reaction time and temperature produced pure phase polypyrrole with high yield and good conductivity. Synthesized polypyrrole by our eco-friendly and cost-effective technique exhibits prominent electromagnetic shielding effectiveness value of 30 dB in the X-band (8–12 GHz).     

Gas phase reaction kinetics in boron fibre production

In the production of boron fibres using the chemical vapor deposition (CVD) technique, boron deposition and dichloroborane formation reactions occurs simultaneously. Boron deposition reaction occurs at the surface, whereas the formation of dichloroborane is the result of both gas phase and surface reactions. A continuous stirred tank reactor (CSTR) type of reactor was designed to investigate the reaction kinetics and kinetic parameters in the gas phase reactions of boron trichloride and hydrogen. It was concluded that reaction rate of the product increased with an increase in the inlet concentration of both reactants (BCl₃ and H₂) and with an increase in the reactor temperature. While reaction order with respect to BCl₃ was almost constant at about 0.5 at each temperature, reaction order with respect to hydrogen increased significantly at temperatures lower than 350°C. A general rate expression was derived for BHCl₂ formation from BCl₃ and hydrogen. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Initiation of cationic polymerization with alcohol/Lewis acid systems

Alcohols in conjunction with BCl₃ have been found to be efficient initiating systems for the polymerization of isobutylene in CH₂Cl₂ solvent. The following alcohols exhibited high initiating activity: tert.-butanol, 1,1-diphenyl ethanol, 2-phenyl-2-propanol, benzhydrol. The organic moiety of the alcohol becomes the head-group of the polyisobutylene formed. The tailgroup of the polymer is a tertiary chlorine most likely because termination is by chlorination by the BCl₃OH^Θ counter anion.     

The influence of In2O3 on electrical characteristics of iron mixed Li2O–PbO–B2O3–SiO2–Bi2O3 multi-component glass system

Glasses of the composition 19Li₂O–20PbO–20B₂O₃–30SiO₂–(10−x) Bi₂O₃–1Fe₂O₃: xIn₂O₃ with six values of x (0 to 5.0) were synthesized. Dielectric properties viz., dielectric constant, ε′(ω), loss, tan δ, ac conductivity, σ_ac, electric modulus, M(ω) over wide ranges of frequency and temperature and also dielectric break down strength have been studied as a function of In₂O₃ concentration. The temperature dispersion of real part of dielectric constant, ε′(ω) has been analyzed using space charge polarization model. The dielectric loss (and also the electric moduli) variation with frequency and temperature exhibited relaxation effects and these effects were attributed to the divalent iron ion complexes. The ac conductivity exhibited maximal effect, whereas the activation energy for the conductivity demonstrated minimal magnitude at about 1.0 mol% of In₂O₃. The conductivity mechanism is understood due to the polaronic transfer between Fe²⁺ and Fe³⁺ ions. The low temperature ac conductivity mechanism is explained following the quantum mechanical tunneling model. Spectroscopic studies viz., optical absorption and ESR spectra have revealed that the redox ratio (Fe²⁺/Fe³⁺) is maximal when the concentration of In₂O₃ is ~1.0 mol%. The higher values of dielectric parameters observed at 1.0 mol% of In₂O₃ are attributed to the presence of iron ions largely in divalent state and act as modifiers. The analysis of these results together with spectroscopic studies has indicated that when In₂O₃ is present in the glass matrix in higher concentrations (more than 1.0 mol%) iron ions predominantly exist in trivalent state, occupy substitutional positions and make the glass more rigid. Such enhanced rigidity of the network is causing the decrease of dielectric parameters with the concentration of In₂O₃. Finally it is concluded that In₂O₃ mostly participate in the glass network in octahedral positions and make act as reducing agent (for iron ions) in the studied glass matrix when its concentration is ≤1.0 mol%.     

Theoretical study on a kind of cyclization mechanism of boron trichloride and hexamethyldisilazane to form the borazine ring for SiBCN ceramics precursor

Borazine rings act as a pivotal part in siliconboroncarbonitride ceramics (SiBCN) for high-temperature stability and great resistance to crystallization. A detailed investigation of the ring formation mechanism will guide the design and synthesis of SiBCN to meet application requirements under extreme conditions. Boron trichloride (BCl₃) and hexamethyldisilazane (HN(SiMe₃)₂) are common raw materials for the synthesis of precursors for SiBCN. In this paper, quantum chemical calculation was used to study the cyclization reaction mechanism between BCl₃ and HN(SiMe₃)₂ to form trichloroborazine (TCBZ) at the MP2/6-31G (d,p) level of theory. We discussed the structure properties, reaction pathways, energy barriers, reaction rates, and other aspects in detail. The results show that BCl₃ and HN(SiMe₃)₂ alternately participate in the reaction process, accompanied by the release of trimethylchlorosilane (TMCS), and that the entire reaction shows an absolute advantage in terms of energy. In the Step by step reaction, lower reaction barriers are formed due to the introduction of BCl₃ with more heat released compared to that for the introduction of HN(SiMe₃)₂. The final single-molecule cyclization and TMCS elimination steps are found to be faster compared to all previous bimolecular reactions.     

High dielectric constant of NiFe2O4–LaFeO3 nanocomposite: Interfacial conduction and dielectric loss

Materials exhibiting colossal dielectric constant are the most sought-after materials due to their variety of applications in various electronics industries. NiFe₂O₄ and LaFeO₃ belonging to the spinel and perovskite structures, respectively, were coupled into a nanocomposite by adapting a one-pot sol-gel synthesis. The ratio of NiFe₂O₄:LaFeO₃ was varied and the synthesized materials were studied for their dielectric behaviors. Interestingly, among the samples studied, the nanocomposite with the ratio of 1:2 of NiFe₂O₄–LaFeO₃ exhibited a high dielectric constant value of 10390 at a frequency of 1 kHz with a several-fold increase in conductivity. The high conductivity resulted in a high dielectric loss. The origin of such a high dielectric constant and loss have been attributed to the Maxwell-Wagner type space charge polarization arising from the microstructure that consists of large and continuous grain boundaries, and the conducting phase at the interface, respectively.     

Preparation of high‐k composites with low dielectric loss based on the double‐layer coaxial structure of inorganic/polymer

This study presents a novel and simple modification of cladding multiwalled carbon nanotubes (MWCNTs) using organic polymer and inorganic nanoparticles to synthesize a product, which has a double‐cladding coaxial structure and can be applied as filler in the dielectric field. The first layer of MWCNTs was coated with polyaniline (PANI) through the oxidation–reduction reaction mechanism using Ce(NH₄)₂(NO₃)₆ as oxidizing agent and metal precursor of cerium oxide. Cerium ions on the second cladding layer of MWCNTs were directly deposited from the solution to the surface of the PANI layer forming the double‐cladding hybrid (CeO₂/PANI@MWCNTs). The external inorganic layer provides an insulating shell, which can prevent the contact between the conductive particles and hinder the migration of electrons between the MWCNTs. The intermediate layer of PANI provides the bonding between CeO₂ and the conductive core of MWCNTs, which also shows lower conductivity than carbon nanotubes. The CeO₂/PANI@MWCNTs were compounded with epoxy (EP) resin and formed a dielectric material with the advantage of reducing dielectric loss while ensuring high dielectric constant. The dielectric constant of the coated MWCNTs/EP composites was 194.90 at 10³ Hz with the content of fillers reaching 30 wt %, which is 28 times that of the pure EP. Accordingly, the dielectric loss of 30 wt % coated MWCNTs/EP composites was only 0.09 at 10³ Hz, which is only 2.25 times that of the pure EP. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46299.