Preparation of phosphinated bisphenol from acid‐fragmentation of 1,1,1‐tris(4‐hydroxyphenyl)ethane and its application in high‐performance cyanate esters

We reveal a route for the preparation of phosphinated bisphenol, 1,1‐bis(4‐hydroxyphenyl)‐1‐(6‐oxido‐6H‐dibenz <c,e> <1,2> oxaphosphorin‐6‐yl)ethane (2) , via a one‐pot reaction of 1,1,1‐tris(4‐hydroxyphenyl)ethane and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) in the catalysis of p‐toluenesulfonic acid. A two‐step reaction mechanism, acid‐fragmentation of 1,1,1‐tris(4‐hydroxyphenyl)ethane followed by nucleophilic addition of DOPO, is proposed for the synthesis. Based on (2) , a dicyanate ester derivative, 1,1‐bis(4‐cyanatophenyl)‐1‐(6‐oxido‐6H‐dibenz <c,e> <1,2> oxaphosphorin‐6‐yl)ethane (3) was prepared and co‐cured with a commercially available dicyanate ester, the dicyanate ester of bisphenol A (BACY). Experimental data show that incorporating (3) into BACY enhances the flame retardancy and dielectric properties with little penalty to the thermal properties. A thermoset with T_g 274 °C, coefficient of thermal expansion (CTE) 49 ppm/°C, D_k 3.04 (1 GHz), T_d (5%,) N₂: 435 °C, air: 424 °C, and UL‐94 V‐0 rating can be achieved via this approach. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

A new representation of permittivity versus temperature for alkanols of the same chain length

The alkanols of three carbon length have been studied by dielectric methods during many years and they do not obey any theoretical model. These substances have the same chain length and have one, two or three dipoles per molecule, so their ability to form hydrogen bridges changes from one substance to other, and one can obtain information by comparative studies. In previous works, we have measured the thermal dependence of permittivity of these substances and analysed the results with an empirical modification of the Onsager equation. Now we shall analyse and compare the results using a different representation. In this representation, the data shows straight lines, whose slopes depend on the quantity of dipoles of each molecule encouraging the high quality of the fittings obtained with the three substances, and also that they behave in the same dielectric way with the rise of temperature.     

Dielectric,thermal, and mechanical properties of CeO2‐filled HDPE composites for microwave substrate applications

Cerium oxide‐filled high density polyethylene (HDPE) composites for microwave substrate applications were prepared by sigma‐blend technique. The HDPE was used as the matrix and the dispersion of CeO₂ in the composite was varied up to 0.5 by volume fraction, and the dielectric properties were studied at 1 MHz and microwave frequencies. The variations of thermal conductivity (k_eff), coefficient of thermal expansion (α_c) and Vicker's microhardness with the volume fraction of the filler were also measured. The relative permittivity (ε_eff) and dielectric loss (tan δ) were found to increase with increase in CeO₂ content. For 0.4 volume fraction loading of the ceramic, the composite had ε_eff = 5.7, tan δ = 0.0068 (at 7 GHz), k_eff = 2.6 W/m °C, α_c = 98.5 ppm/°C, Vicker's microhardness of 18 kg/mm² and tensile strength of 14.6 MPa. Different theoretical approaches have been used to predict the effective permittivity, thermal conductivity, and coefficient of thermal expansion of composite systems and the results were compared with the experimental data. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 998–1008, 2010     

Molecular motion and interactions in aqueous carbohydrate solutions. I. Dielectric-relaxation studies

Dielectric-relaxation studies in the frequency range 200 kHz to 35 GHz are reported for a range of sugars (from mono- to trisaccharides) in aqueous solution. The complex dielectric spectra were analyzed using a weighted least-squares minimization method to resolve the various component relaxations, and the implications of the analyses in terms of the molecular dynamics of solute and solvent and the interactions between solute and solvent are discussed. For the highest concentration studied (ca. 2M), it was found that the most significant analysis required three discrete relaxation processes, whereas lower concentration samples could usually be satisfactorily fitted with two. Irrespective of any uncertainty in model selection, a number of conclusions regarding the solute-solvent interactions can be made, and it is shown how final quantification of the extents of hydration can be made using the input of information from other techniques.     

Studies on Poly(Dialkoxyphosphazenes) for the Medical Applications

Abstract

The presence of trace of chlorine in poly(diorganophosphazenes) [-N=P(OR)2-]., where R = C₂H₅, CH₂CF₃, C₂F₅, C₄H₅, C₆H₁₃, C₈H₁₇, C₁₂H₂₅, CH₂C₆H₅ in many cases leads to the substantial changes of their physicochemical properties and limits application possibilities of this class of polymers especial for the medical materials. Despite the optimization of reaction conditions for each nucleophilic alkoxy substituent, the obtained poly(dia1koxyphosphaenes) exhibited some physicochemical anomalies.     

Synthesis,Characterization and Comparison of Properties of Novel Fluorinated Polyimides Derived from Bisphenol–A‐di(phthaleic anhydride)

Four new poly(etherimide)s have been synthesized by reaction with commercially available bisphenol‐A‐(diphthaleic anhydride) (BPADA) with four different kinds of diamines, namely 4,4′‐bis(p‐aminophenoxy‐3,3″‐trifluoromethyl) terphenyl,4,4′‐bis(3″‐trifluoromethyl‐p‐aminobiphenyl ether)biphenyl,2,6‐bis(3′‐trifluoromethyl‐p‐aminobiphenyl ether)pyridine, 2,5‐bis(3′‐trifluoromethyl‐p‐aminobiphenylether)thiopene. The poly(etherimide)s are named as 1a, 1b, 1c and 1d, respectively. The synthesized polyimides show good solubility in various organic solvents. The polyimide films had low water absorption of 0.19–0.30% and low dielectric constant of 2.79–3.1 at 1 MHz. These polyimides showed very high thermal stability with decomposition temperature (5% wt loss) up to 522°C in nitrogen. Transparent thin films of these polyimides exhibited tensile strength up to 97 MPa, a modulus of elasticity up to 1.56 GPa and elongation at break up to 20%.     

Synthesis and Properties of Poly(Aryl Ether Ketone) Copolymers with Trifluoromethyl‐Substituted Benzene in the Side Chain

The new monomer (4‐(4′‐trifluoromethyl)phenoxyphenyl)hydroquinone (TFPOPH) was synthesized in a three‐step synthesis. A series of poly(aryl ether ketone) copolymers were prepared by the reaction of (4‐(4′‐Trifluoromethyl)phenoxyphenyl)hydroquinone and hydroquinone (HQ) with 4,4′‐difluorobenzophenone (DFB) in the presence of potassium carbonate in tretramethylene sulfone (TMS). Thermal analyses of the fluorinated copolymers showed that the glass transition temperature and 5.0% weight loss temperature are similar with that of PEEK, and the crystallinity decreased with increasing of TFPOPH. For the copolymer synthesized with the molar fraction of TFPOPH in the diphenol monomers (TFPOPH, HQ) being over 0.2, no cold crystallization temperature and melting temperature were detected, indicating that these copolymers are almost amorphous. The crystal structure of the copolymers with the molar fraction of TFPOPH being not higher than 0.2 is rhombic. The solubility in polar aprotic solvents of poly(aryl ether ketone)s copolymers increases and dielectric constant decreases step by step.     

Evaluation of the (Allyl alcohol 1,2‐butoxylate‐block‐etoxylate)‐b‐PMMA Copolymers Composition by the Dielectric Measurements

Redox initiated free‐radical polymerization of methyl methacrylate (MMA) with allyl alcohol 1,2‐butoxylate‐block‐etoxylate (AABE) was carried out to yield AABE‐b‐PMMA copolymers at elevated temperatures. The composition of the copolymers depending on the polymerization temperature was qualitatively estimated by the dielectric measurements. It has been seen that AABE segment quantity decreased and PMMA segment quantity increased with increasing the polymerization temperature. The dielectric constant and the dissipation factor of the copolymers were investigated as a function of frequency and temperature. The dielectric constant and the dissipation factor were found to be strongly affected by the polymerization temperature. The highest dielectric constant in all studied temperatures and frequencies was obtained in the case of the copolymer which was prepared at 313 K. The dipolar C‐O and OH groups of the AABE segment have the primary effect on the dielectric constant. The copolymer which was prepared at 323 K, showed the highest dissipation factor near the relaxation temperature of PMMA.     

Silver Nanoparticles in Polyacrylamide and Hyperbranched Polyamine Matrix

Silver nanoparticles have been prepared in a polyacrylamide (PA) matrix, as well as in the presence of a hyperbranched polyamine/polyacrylamide combined system (HB‐PA) by using a reductive technique. The stability of colloidal solution of silver nanoparticles is higher (5 months) in combined matrix compared to PA alone (4 months). The prepared silver nanoparticles were characterized by different spectroscopic and analytical techniques such as FTIR, UV‐visible, X‐ray diffraction, TEM etc. TEM and XRD studies confirmed the formation of well‐dispersed nanoparticles with an average size of 9.91 nm and 8.5 nm for PA and HB‐PA matrices, respectively. The antibacterial activity of silver nanoparticles in both the matrices was tested against Bacillus Subtilis bacteria by using the diffusion disc technique. The result shows that the antibacterial activity of the active agent, Ag(0) is a little higher in the case of HB‐PA system. The dielectric constant of the matrices decreases with an increase in frequency, but the values increase with an increase of concentration of silver nanoparticles in PA matrix.     

Synthesis and characterization of fluorine functionalized graphene oxide dispersed quinoline-based polyimide composites having low-k and UV shielding properties

Polyimide nanocomposites having low-k and UV shielding properties have been developed using fluorine functionalized graphene oxide and bis(quinoline amine) based polyimide. The polyimide was synthesized using bis(quinoline amine) and pyromellitic dianhydride at appropriate experimental conditions, and its molecular structure was confirmed through various spectral analysis such as FTIR and NMR. The polyimide (PI) composites were prepared using bis(quinoline amine), pyromellitic dianhydride, and separately filled with 1, 5, 10 wt% of fluorinated graphene oxide (FGO) through in situ polymerization. The polymer composites were characterized using thermo gravimetric analysis (TGA), X-ray powder diffraction (XRD), and scanning electron microscopy (SEM). In addition, the water contact angle, dielectric behavior, and UV–Vis shielding behavior of FGO/PI composites were evaluated. The value of the water contact angle of the polyimide was increased with increment of FGO in the polyimide matrix. The highest water contact angle of polyimide composites observed 108° was obtained for 15 wt% FGO reinforced polyimide composite. The value of the dielectric constant for neat, 1, 5, and 15 wt% FGO reinforced polyimide composites was obtained as 4.5, 3.7, 2.6, and 2.0, respectively. It is also observed from by UV–Vis spectroscopy analysis that the FGO reinforced polyimide composites have good UV shielding behavior.