Hydroxy Ether Of bisphenol-A Research Articles

Chemical Interaction-Induced Evolution of Phase Compatibilization in Blends of Poly(hydroxy ether of bisphenol-A)/Poly(1,4-butylene terephthalate).

An immiscible blend of poly(hydroxy ether of bisphenol-A) (phenoxy) and poly(1,4-butylene terephthalate) (PBT) with phase separation was observed in as-blended samples. The compatibilization of phenoxy/PBT blends can be promoted through chemical exchange reactions of phenoxy with PBT upon annealing. The annealed phenoxy/PBT blends had a homogeneous phase with a single Tg that could be enhanced by annealing at 260 °C. Infrared (IR) spectroscopy demonstrated that phase homogenization could be promoted by annealing the phenoxy/PBT blend, where alcoholytic exchange occurred between the dangling hydroxyl group (–OH) in phenoxy and the carbonyl group (C=O) in PBT in the heated blends. The alcoholysis reaction changed the aromatic linkages to aliphatic linkages in the carbonyl groups, which initially led to the formation of a graft copolymer of phenoxy and PBT with an aliphatic/aliphatic carbonyl link. The progressive alcoholysis reaction resulted in the transformation of the initial homopolymers into block copolymers and finally into random copolymers, which promoted phase compatibilization in blends of phenoxy with PBT. As the amount of copolymers increased upon annealing, the crystallization of PBT was inhibited by alcoholytic exchange in the blends.

Enhancing the Compatibility of Poly (1,4-butylene adipate) and Phenoxy Resin in Blends.

This work concerns the enhancement in the compatibility of blends of poly (1,4-butylene adipate) (PBA) with poly (hydroxy ether of bisphenol-A) (phenoxy) via alcoholytic exchange. Results on the thermal behavior and morphology show that the blended PBA/phenoxy system exhibits a homogeneous phase and a composition-dependent glass transition temperature (Tg). The interaction parameter (χ12) of PBA/phenoxy blends was calculated using the melting point depression method and was found to be −0.336. However, the compatibilization of PBA/phenoxy blends can be enhanced by chemical exchange reactions between PBA and phenoxy upon annealing. Annealed PBA/phenoxy blends were found to have a homogeneous phase with a higher Tg than that of the blended samples, and a smooth surface topography that could be improved by annealing at high temperature. The results of this investigation demonstrate that promotional phase compatibilization in the PBA/phenoxy blend can only be obtained upon thermal annealing, thus causing transreactions to occur between the dangling –OH of the phenoxy and the ester functional groups in PBA. Extensive transreactions cause alcoholytic exchange between the PBA and phenoxy to form a network, thus reducing the mobility of the polymer chain. Finally, the crystallinity of PBA decreased as the degree of transreaction in the blends increased.

Chemical Exchange Reactions in Blends of the Biodegradable Polyester with poly(hydroxy ether of bisphenol-A)

Compatibilization via transreactions in blends of poly (butylene succinate-co-butylene terephthalate) [P(BS-co-BT)] with poly (hydroxy ether of bisphenol-A) (phenoxy) were investigated. Analyses were based on characterization using differential scanning calorimetry (DSC) and solid-state nuclear magnetic resonance (NMR). They revealed that the P(BS-co-BT)/phenoxy blend had a phase morphology that could be homogenized only following annealing at high temperatures. As-blended P(BS-co-BT)/phenoxy (50/50 composition) exhibited immiscible phases with two distinct Tgs, but the initially phase separated blends finally merged to form a homogeneous phase with a single Tg upon heating and annealing for 60 min at 280 °C. Chemical exchange reactions upon heat-annealing were likely to have caused the phase homogenization in the P(BS-co-BT)/phenoxy blend. NMR was performed on blend samples before and after they were heated to 280 °C, but the similarity of bonds made obtaining straight results difficult. Results of this study demonstrate phase homogenization can be brought only upon heat-annealing in the P(BS-co-BT)/phenoxy blend.

Thermal and thermo-oxidative degradation of poly(hydroxy ether of bisphenol-A) studied by TGA/FTIR and TGA/MS

The nature and the extent of degradation of poly(hydroxy ether of bisphenol-A) phenoxy resin were analysed by thermogravimetry (TGA/DTGA) under nitrogen and air atmosphere. Decomposition kinetics were elucidated according to Flynn–Wall–Ozawa, Friedman and Kissinger methods. The evolved gases during degradation were inspected by a thermogravimetry analyser coupled with Fourier Transform Infrared Spectrometer (TGA/FTIR) and also with a TGA coupled to a Mass Spectrometer (TGA/MS). Mass spectra showed that chemical species evolved in phenoxy decomposition in air were very similar to those assigned from degradation in nitrogen (water, methane, CO, CO 2, phenol, acetone, etc.). However, these species appear in different amount and at different temperatures in both atmospheres. FTIR analysis of the evolved products showed that water and methane were the beginning decomposition products, indicating that decomposition is initiated by dehydration and cleavage of C–CH 3 bond in the bisphenol-A unit of phenoxy resin. After this initial stage, random chain scission is the main degradation pathway. Nevertheless, in air atmosphere, previously the complete decomposition of the phenoxy obtaining fundamentally CO 2, and water, the formation of an insulated surface layer of crosslinked structures has been proposed.

Enhancement of stiffness, strength, ductility and toughness of poly(ethylene oxide) usingphenoxy-grafted multiwalled carbon nanotubes

Phenoxy (poly(hydroxyether of bisphenol-A), also known aspoly(bisphenol-A-co-epichlorohydrin)) was grafted onto multiwalled carbon nanotubes (MWNTs) by a reactiveblending process. Reactions between terminal glycidyl groups of phenoxy andcarboxylic acid groups of acidified MWNTs resulted in the grafting of phenoxy chainsonto MWNTs. The mechanical properties of composites of poly(ethylene oxide)(PEO) and phenoxy-grafted MWNTs were studied. The miscibility between PEOand phenoxy enabled the good dispersion of nanotubes in the PEO matrix asevidenced by polarized optical microscopy and transmission electron microscopy.The spherulite size of PEO progressively decreased with increasing amount ofphenoxy-grafted MWNTs added. At an optimal MWNT content of 1.5 wt%, the addition ofphenoxy-grafted MWNTs led to increases of storage modulus, Young’s modulus,yield stress, tensile strength, ultimate strain, and toughness of PEO by 113, 228,166, 442, 1240, and 4080%, respectively. Such simultaneous increases in stiffness,strength, ductility and toughness of a polymer by an additive are rather uncommon.

Microstructure of copolymers obtained from chemical modification of phenoxy resin: a13C NMR study

The microstructure of a series of copolymers obtained from the chemical modification of poly(hydroxy ether of bisphenol-A) (phenoxy resin) with different degrees of modification has been investigated by 1H and 13C NMR spectroscopy. In the 13C spectra, the resonance due to all quaternary carbons of bisphenol-A unit appear to be sensitive to the compositional sequence distribution of the copolymer and exhibit clear diad splitting. The experimentally determined average sequence length is found to be in accord with ideal random distribution statistics with randomness close to unity. These results could be useful in the study of the microstructure of other phenoxy modifications, in polymer blends based on phenoxy and epoxy resins where trans reactions can occur. They could also be useful in the determination of the branching microstructure of bisphenol-A based epoxy resins. © 2000 Society of Chemical Industry

The study of miscibility and phase behaviour of phenoxy blends using Raman spectroscopy

The miscibility and phase behaviour of poly(hydroxy ether of bisphenol-A) (phenoxy)/poly(methyl methacrylate) (PMMA) blends were investigated using Raman microscopy. It was shown that while phenoxy/PMMA blends prepared by casting from chloroform at room temperature are immiscible, the blends prepared at high temperature are miscible. The Raman technique revealed the shift of the PMMA carbonyl stretching band in the miscible blends and its absence in the immiscible blends. This may be explained by the presence of specific interactions between the groups in phenoxy and PMMA due to the increased chain mobility during the mixing at high temperature. The changes of the special features in the Raman spectra were found to be useful in identifying different phase structures and their compositions in the blends.

Miscibility and interpolymer complexation of poly(1-vinyl-imidazole) with hydroxyl- and carboxyl-containing polymers

The miscibility of poly(1-vinylimidazole) (PVI) with some hydroxyl- and carboxyl-containing polymers was studied. Each of the binary blends or complexes of PVI with poly(p-vinylphenol) (PVPh), poly(2-hydroxypropyl methacrylate) (PHPMA) and poly(acrylic acid) (PAA) showed a single glass transition temperature (T g ), indicating miscibility. However, PVI is immiscible with poly(styrene-co-allyl alcohol) (SAA) and poly(hydroxyether of bisphenol-A) (Phenoxy) as shown by the appearance of two T g 's in each of the blends. Based on the frequency shifts of the hydroxyl band of the hydroxyl-containing polymers, the intensities of hydrogen bonding interactions between PVI and hydroxyl-containing polymers are in the order PVPh > PHPMA > SAA and Phenoxy. PVI interacts with PAA via ionic interaction.

A closed-loop phase behaviour of ternary homopolymer blend composed of three miscible binaries

The phase behaviour of ternary polymer blend of poly(methyl methacrylate) (PMMA), poly(ethylene oxide) (PEO) and poly(hydroxy ether of bisphenol-A) (phenoxy) was investigated. Although all three binary blends are separately miscible, there exists a closed immiscibility loop in the phase diagram of ternary blends. It may result from small differences in the interaction energy of binary systems, the so-called ‘Δχ effect’. The value of χ phenox/PMMA, by comparing the theoretically predicted phase diagram with experimental data, was determined to be −0.61.

Complexation between poly(hydroxyether of bisphenol-A) and three tertiary amide polymers

The complexation behaviour between poly(hydroxyether of bisphenol-A) (phenoxy) and three isomeric tertiary amide polymers, namely poly(N-methyl-N-vinylacetamide) (PMVAc), poly(N,N-dimethylacrylamide) (PDMA) and poly(2-ethyl-2-oxazoline) (PEOx), has been studied. Phenoxy forms interpolymer complexes with PMVAc and PDMA from tetrahydrofuran solutions over the entire feed composition range. However, complexation does not occur between phenoxy and PEOx from THF solutions, indicating a weaker intermolecular association in the phenoxy/PEOx blends than those in the phenoxy/PMVAc and phenoxy/PDMA blends. When using N,N-dimethylformamide as the solvent, only miscible blends are formed between phenoxy and all three tertiary amide polymers. Infra-red spectroscopic studies provide evidence of intermolecular hydrogen bonding between the hydroxyl groups in phenoxy and the carbonyl groups in tertiary amide polymers. The frequency shifts for the phenoxy hydroxyl group hydrogen bonded to the three tertiary amide polymers decrease in the order of PMVAc → PDMA → PEOx.

Non-isothermal crystallization of poly(hydroxy ether of bisphenol-A)/poly(ϵ-caprolactone), PH/PCL blends

The non-isothermal crystallization from the melt of the poly(hydroxy ether of bisphenol-A)/poly(ϵ-caprolactone) (PH/PCL) miscible blend was studied. Cooling rates between 0.31 and 20°C min−1 were used. At a given cooling rate, the presence of PH reduces the overall PCL crystallization rate. For a given composition, the crystallization process beings at higher temperatures when slower scanning rates are used. The experimental data analysis shows agreement with both Ozawa and Avrami treatments, and agrees quite well with the theoretical results obtained using the Ziabicki method. Non-isothermal crystallization results of PH/PCL blends are compared with those reported in a previous paper studying the isothermal crystallization for the same system.

Miscibility and interpolymer complexation of poly(2-methyl-2-oxazoline) with hydroxyl-containing polymers

Poly(2-methyl-2-oxazoline) (PMOx) was found to be miscible with poly (styrene-coallyl alcohol), poly(hydroxyether of bisphenol-A), poly (2-hydroxypropyl methacrylate) and poly(p-vinylphenol) (PVPh), when cast from N,N-dimethylformamide solutions and to form interpolymer complexes with PVPh in methanol solutions. The hydrogen bonding interactions between PMOx and hydroxyl-containing polymers were studied by infrared spectroscopy and compared with the corresponding blends of poly(2-ethyl-2-oxazoline) (PEOx). Except with phenoxy, PMOx interacts more strongly with hydroxyl-containing polymers than PEOx does.

Interpolymer Complexation and Blend Formation between Poly(N-vinyl-2-pyrrolidone) and Aliphatic Hydroxyl-Containing Polymers

The interpolymer complexation and blend formation between poly(N-vinyl-2-pyrrolidone) (PVP), a tertiary amide polymer, and three aliphatic hydroxyl-containing polymers, namely, poly(2-hydroxypropyl methacrylate), poly(hydroxyether of bisphenol-A) and poly(styrene-co-allyl alcohol), has been studied. PVP forms interpolymer complexes with all the three aliphatic hydroxyl-containing polymers in tetrahydrofuran solutions over the entire feed composition range. The glass transition temperatures of the complexes are higher than those calculated from the additivity rule. PVP has a stronger ability in forming interpolymer complexes with aliphatic hydroxyl-containing polymers than the other three tertiary amide polymers, namely, poly(N-methyl-N-vinylacetamide), poly(N,N-dimethylacrylamide), and poly(2-ethyl-2-oxazoline). Infrared spectroscopic studies show that the hydrogen bonding interactions between the carbonyl groups in PVP and the hydroxyl groups are stronger than the self-associations of the hydroxyl-containing polymers. Semiempirical Austin Model 1 (AM1) calculations reveal that the atomic charges of the carbonyl oxygen atoms of all these tertiary amide polymers are about the same, suggesting that steric factor is important in determining their complexation behavior.

Influence of the Blending Method and Poly(methyl methacrylate) Tacticity in Its Miscibility with Poly(hydroxy ether of bisphenol A, phenoxy)

Blends of poly(hydroxy ether of bisphenol-A) (phenoxy) and poly(methyl methacrylate) exhibit a different phase behaviour depending on the blending method. Additionally, both polymers present similar glass transition temperatures complicating the study of the phase behaviour by classical DSC methods. The problem has been resolved by using different experimental techniques (enthalpy relaxation, DMTA, CP-MAS NMR) which have confirmed the intrinsic miscibility of this blend. The influence of the poly(methyl methacrylate) tacticity in the miscibility of the blends has also been studied.

Complexation between poly(2‐hydroxypropyl methacrylate) and three tertiary amide polymers

AbstractThe complexation behavior between poly(2‐hydroxypropyl methacrylate) (PHPMA) and three isomeric tertiary amide polymers, namely, poly(N‐methyl‐N‐vinylacetamide) (PMVAc), poly(N,N‐dimethylacrylamide) (PDMA), and poly(2‐ethyl‐2‐oxazoline) (PEOx), was studied. PHPMA forms interpolymer complexes with the three tertiary amide polymers at the entire feed composition range in methyl ethyl ketone and tetrahydrofuran solutions, indicating a strong intermolecular interaction between different polymer chains. However, complexation does not occur between PHPMA and the three tertiary amide polymers in N,N‐dimethylformamide solutions. Infrared spectroscopic studies show that the intermolecular hydrogen bonding association between the hydroxyl groups in PHPMA and the amide carbonyl groups in the tertiary amide polymers is stronger than the self‐association between the hydroxyl groups and the ester carbonyl groups in PHPMA. PHPMA has a stronger complexation ability with these tertiary amide polymers than poly(styrene‐co‐allyl alcohol) and poly(hydroxyether of bisphenol‐A) do. © 1994 John Wiley & Sons, Inc.

Phenoxy and diglycidyl ether of bisphenol-A as compatibilizers for nylon 6/methyl methacrylate-styrene-butadiene graft polymer blends

Poly(hydroxy ether of bisphenol-A) (phenoxy resin) and diglycidyl ether of bisphenol-A type epoxy resin (DGEBA) are found to be excellent compatibilizers for polyamide 6 (nylon 6)/methyl methacrylate-styrene-butadiene (MBS) graft polymer blends. When the blends are modified by phenoxy of DGEBA, phase dispersion, mechanical properties and rheological properties are significantly improved. The compatibility between phenoxy and MBS is based on thermodynamic miscibility between phenoxy and poly(methyl methacrylate) in MBS. The compatibility between nylon 6 and phenoxy seems to originate from the reactivity between functional groups of the two polymers. The compatibility between DGEBA and MBS is also based on thermodynamic miscibility between the chain component of the epoxy and poly(methyl methacrylate) in MBS. The compatibility between nylon 6 and the epoxy resin originates from reactivity between the functional groups of the two polymers. The role of phenoxy or DGEBA as compatibilizers in nylon 6/MBS blends is demonstrated and the two compatibilizers are compared.

Inverse gas chromatography in the characterization of polymeric materials

Different experimental results are presented for the use of inverse gas chromatography in the determination of the physico-chemical properties of pure polymers, polymer solutions and polymer blends. Using poly(hydroxy ether of bisphenol-A) (Phenoxy), its solutions and its blends with other polymers, thermal transitions, polymer solubility parameters, polymer-solvent and polymer-polymer interaction parameters and diffusion coefficients of small molecules in pure Phenoxy have been measured by inverse gas chromatography.

Mechanical properties of ternary blends of poly(butylene terephthalate), bisphenol-a-polycarbonate and poly(hydroxyether of bisphenol-A)

Ternary poly(butylene terephthalate) (PBT)/bisphenol-A-polycarbonate (PC)/poly(hydroxyether of bisphenol-A) (phenoxy) blends, with PBT contents from 0 to 30% were obtained by melt-mixing. The presence of PBT clearly increases the ductility of the already rather ductile PC/phenoxy blends. The increase of ductility was accompanied by a slight synergism in the yield stress and by a very small change of the modulus of elasticity of the blends with PBT as compared to those without PBT. The observed fracture surface shows a ductile fracture with two phases without signs of debonding between them. It is established that a third polymeric component present in both phases of an immiscible blend may have a beneficial effect on the mechanical properties of the blend.

Relationship between the time-domain Kohlrausch-Williams-Watts and frequency-domain Havriliak-Negami relaxation functions.

The Kohlrausch-Williams-Watts (KWW) and the Havriliak-Negami (HN) relaxation functions have been widely used to describe the relaxation behavior of glass-forming liquids and complex systems. While the HN relaxation function is a frequency function, the natural domain of the KWW relaxation function is time (although it has also been used with frequency-domain spectroscopies). A relationship among the parameters of the two models is suggested by the fact that both models yield an accurate description of real data. Nevertheless, this relationship cannot be an analytical one, since it is known that the HN and the KWW relaxation functions are not exactly Fourier transforms of each other. In order to find out the nature of this relationship, a method which makes use of a distribution of relaxation times is proposed here. Numerical simulations following the KWW model have been assumed to describe the relaxation behavior in time; likewise, the HN description was assumed to be valid for the frequency domain. From this work, a connection among the parameters of both models is obtained, which is expected to be valid for those experimental data that can be described by either the KWW or the HN model. This is the case for most, if not all, measurements on the dynamics in complex systems and glass-forming liquids that frequently appear in the literature. The proposed procedure has been tested by using dielectric-spectroscopy measurements, both in frequency and time domains to study the \ensuremath{\alpha} relaxation in a glass-forming polymeric system, poly(hydroxy ether of bisphenol-A).

Polyurethanes from 2,4-toluene diisocyanate and a mixture of castor oil and hydroxyether of bisphenol-A

Polyurethanes (PU) were prepared from 2,4-toluene diisocyanate (TDI) and mixtures of castor oil and hydroxyether of bisphenol-A (HBA). Differential scanning calorimetry and dynamic mechanical measurements studies revealed that each PU so obtained has a single T 8s, increasing with both HBA content and ratio of NCO/OH from 0.85 to 1.1. With increasing HBA/[HBA + castor oil]from 0 to 0.50, the PU samples exhibit various modes of fracture, from the common stress-strain behaviour of elastomers to ductile fracture and to brittle fracture while the Young's modulus increases almost by three orders of magnitude. The curves of Young's modulus vs HBA/[HBA + castor oil] are S-shaped, implying that the PUs are not molecularly homogeneous. Tensile strength increases greatly with HBA content. Increasing NCO/OH ratio from 0.85 to 1.1 also enhances the tensile strength. The elongation at break first increases and then decreases with increasing ratio HBA/[HBA + castor oil].