Phase transitions in mesophase macromolecules. III. The transitions in poly(ethylene terephthalate-co-p-oxybenzoate)

The glass and melting transitions of poly(ethylene terephthalate-co-p-oxybenzoate)s have been studied by differential scanning calorimetry. Despite the higher glass transition expected for polyoxybenzoate, there is almost no change in the glass transition temperature up to 63 mol % oxybenzoate (353 ± 4 K). At high oxybenzoate concentration there seems to be a discontinuous jump to a glass transition of 450 K. This high glass transition has been observed in two-phase materials down to 30 mol % oxybenzoate. The melting transition shows signs of isodimorphism with a minimum in melting temperature at about 60–70 mol % oxybenzoate, 60 K below the melting temperature of poly(ethylene terephthalate). The thermal properties are little affected by the change of the noncrystalline parts of the molecules to a mesophase structure. The transition to the isotropic phase could not be analyzed because of prior decomposition.     

Phase transitions in mesophase macromolecules. VI. The transitions in poly(oxy-2,2′-dimethylazoxybenzene-4,4′-diyloxydodecanedioyl)

The transitions of poly(oxy-2,2′-dimethylazoxybenzene-4,4′-diyloxydodecanedioyl) (PDAD) have been analyzed by differential scanning calorimetry, optical microscopy, and light scattering. The mesophase glass devitrifies at 288 K [ΔC_p = 220 J/K mol]. Crystallization from the liquid mesophase can be described between 322 and 362 K by an Avrami expression with an exponent between 3 and 4. Results of light scattering and optical microscopy are in accord with a spherulitic morphology grown after athermal nucleation. Melting of the semicrystalline samples (crystallinity up to 58%) occurs at about 391 K. The heat of fusion of the completely crystalline sample is calculated to be only 13.55 kJ/mol. The mesophase to isotropic phase transition occurs at 418 K with a heat of transition of 4.1 kJ/mol. A general discussion of these transitions is given.     

Transitions and relaxations in poly(1,4-phenylene ether)

Transitions and relaxation phenomena in poly(1,4-phenylene ether) were studied over temperature range from 100 to 800°K by applying a combination of calorimetric, dilatometric, dynamic mechanical, and dielectric techniques. Amorphous polymer, exhibiting no x-ray crystallinity, is obtained only by quenching molten samples at extremely fast cooling rates (ca. 1000°C/sec) and by minimizing thermal gradients within specimens. A weakly active mechanical relaxation region with a loss maximum at 155°K of unknown origin was observed. The glass transition interval of completely amorphous polymer is characterized by a discontinuous jump in heat capacity of 2.76 cal/deg per chain segment occurring at 363°K (corrected for kinetic effects), and a fourfold increase in the coefficient of linear thermal expansion. Strongly active, dynamic mechanical relaxations occur in the T_g interval with a loss maximum at 371°K (f = 110 cps) and resulting in a drop in the dynamic storage modulus from 10¹¹ to 10⁹ dyne/cm². Cold crystallization takes place just above T_g, to yield a polymer with an x-ray crystallinity of 0.7 and a heat of crystallization of 270 cal/mole. The crystalline polymer shows a complex melt structure. Depending upon the thermal history, multiple endothermic peaks indicative of structural reorganizations occur just prior to fusion. Very high dielectric losses with a wide distribution of relaxation times were observed in the melt interval. The mechanical relaxation spectrum in this region is typical of viscous flow behavior.     

Phase transitions in mesophase macromolecules. I. Novel behavior in the vitrification of poly(ethylene terephthalate-co-p-oxybenzoate)

A 40:60 mole ratio poly(ethylene terephthalate-co-p-oxybenzoate) was studied by dynamic scanning calorimetry. Vitrification occurred in two steps, which could be linked by optical microscopy to a two-phase structure. For the lower glass transition, hysteresis was absent on heating and cooling through the transition temperature. Since all prior studied glasses show such hysteresis, this may be linked to the mesophase structure and raises the question whether mesophases always display such glass-transition behavior.     

Phase behavior in copolymer blends of poly (p-chlorostyrene-co-o-chlorostyrene) and phenylsulfonylated poly (2,6-dimethyl-1,4-phenylene oxide)

The miscibility of random copolymers of o-chlorostyrene and p-chlorostyrene [P (oClSt-co-pClSt)] with partially phenylsulfonylated poly (2,6-dimethyl-1,4-phenylene oxide) (SPPO) copolymers has been studied, using differential scanning calorimetry (DSC) to establish T_g behavior. It already has been established that the isomeric effect of the chlorine substitution on miscibility is large. Thus the para-chloro-substituted styrenic homopolymer is miscible with all SPPOs containing more than ～ 5 mol % phenylsulfonylation, whereas the ortho-chloro-substituted homopolymer is immiscible with the entire range of SPPO copolymer compositions (and also with the respective homopolymers). As a result of this asymmetric behavior of the homopolymers, the width of the window of miscibility in blends now investigated containing copolymers with high pClSt content and SPPO is much greater than in the corresponding blends containing copolymers with large mole fraction of oClSt. These differences are reflected in the corresponding χ parameters calculated from analysis of the data. It was also found that the miscibility is temperature dependent and that the regime in the copolymer-copolymer composition plane shrank as the equilibrium temperature increased, results indicative of LCST behavior. © 1994 John Wiley & Sons, Inc.     

Thermal behaviour of poly(2,6-dimethoxy-1,4-phenylene ether)

Thermodynamic properties of semicrystalline and completely amorphous samples of poly(2,6-dimethoxy-1,4-phenylene ether) have been studied by DSC-calorimetry. A very low entropy of fusion indicates that only minor conformational changes take place during the melting. The low value of the configurational entropy of the glass transition is due to the faci that the theoretical second order transition is closely related to the glass transition point.     

Thermodynamic properties of poly(2,6-dimethyl-1,4-phenylene ether)

The thermodynamic properties of crystalline and amorphous poly(2,6-dimethyl-1,4-phenylene ether) (PPO

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polymer, General Electric Co.) have been studied calorimetrically between 80 and 570°K. The calculated configurational entropy of this polymer, of similar magnitude to other glass-forming liquids, is consistent with the combination of an unusually high ratio of T_g/T_m, and a low melting entropy.     

Direct metalation of poly(2,6-dimethyl-1,4-phenylene ether)

Poly(2,6-dimethyl-1,4-phenylene ether) (I) was metalated with butyllithium in tetrahydrofuran and with the N,N,N′,N′-tetramethylethylenediamine complex of butyllithium in a variety of solvents. In these cases, metalation occurred at both the ring and side chain positions, the former being preferred initially. Subsequently, there was an isomerization in favor of the side chain. At 25°C, there is no significant amount of polymer scission or crosslinking during metalation, but some crosslinking occurs on derivatizing with dimethyl sulfate and trimethylchlorosilane for high extents of ring metalation. With sodium and potassium alkyls, only side-chain metalation was observed. The metalated polymer reacts as a typical organometallic, allowing polymer modification by a wide variety of reactions.     

Single crystals of poly(2,6-dimethyl-1,4-phenylene)oxide

Summary Poly(2,6-dimethyl-1,4-phenylene)oxide crystals obtained from 0.1%-pinene solutions by isothermal growth at temperatures from 80–90 as well as 100 °C, were investigated by optical and X-ray diffraction techniques. A study has been made by differential scanning calorimetry in order to measure the melting point, glass transition and melting point depression temperatures of mixtures of the polymer with-chloro-naphthalene.The densities of the dry mats of single crystals were measured by a flotation method.

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Zusammenfassung Poly(2,6-dimethyl-1,4-phenylen)oxid Kristalle, die aus 0,1% igen-Pinen-Lösungen durch isothermes Wachstum bei Temperaturen von 80–90 sowie 100 °C erhalten wurden, wurden optisch und röntgenographisch untersucht. Mit der Differential-scanning-Kalorimetrie ergaben sich die Werte des Schmelzpunkts, der Glastemperatur und der Schmelzpunktdepressionen von Mischungen des Polymeren mit-Chlornaphthalin. Die Dichten der trockenen Matten aus Einkristallen wurde mit der Flotationsmethode gemessen.

     

Unperturbed dimensions of poly(2-methyl-6-phenyl-1,4-phenylene oxide) and poly(2,6-diphenyl-1,4-phenylene oxide) chains

The unperturbed chain dimensions of unfractionated poly(2-methyl-6-phenyl-1,4-phenylene oxide) and poly-(2,6-diphenyl-1,4-phenylene oxide) have been measured by combining molecular weight data from light scattering with intrinsic viscosity data in chloroform. The unperturbed chain dimensions of the former polymer were also measured directly by light scattering dissymmetry in a critical consolute solvent mixture (methyl cyclohexane: 1,4-dioxane 50:50 by volume). The results of these measurements and of measurements reported by other investigators are satisfactorily explained by postulating no dimension-expanding prejudice in azimuthal angle in chain conformers of the 2,6-substituted-1,4-phenylene oxide polymers. This corresponds to equal population of the two chain rotation energy minima at azimuthal angles 90° and 270°. Accepting this postulate, one calculates from the observed chain dimensions that the C? O? C bond angle is 118–120° in these aromatic polyethers in solution.     

The high-temperature degradation of poly(2,6-dimethyl-1,4-phenylene ether)

The thermal degradation of poly(2,6-dimethyl-1,4-phenylene ether) has been investigated to 1000°C in an inert atmosphere. X-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry were employed to study the physical changes in the polymer, and vapor-phase chromatography, infrared spectroscopy, and mass spectrometric thermal analysis were used to elucidate the chemical aspects of the degradation process. It was found that degradation occurs in two steps: (1) a rapid exothermic process occurs between 430 and 500°C, leading to the evolution of phenolic products, water, and a black, highly crosslinked residue, and (2) a slower, char-forming process occurs above 500°C, characterized by the evolution of methane, carbon monoxide, and hydrogen. The chars formed in process 2 were found by x-ray analysis to be amorphous. The infrared spectrum of a sample heated to 510°C is nearly identical with that of the starting polymer, indicating that oxidative reactions are not important in the first process. The data for the low-temperature process are consistent with a thermal degradation scheme based on the radical-redistribution reaction of polyphenylene ethers and/or the degradation of o-benzylphenols formed by the thermal rearrangement of o-methyl diphenyl ethers. The char-forming process is best explained by simultaneous operation of the Szwarc mechanism of toluene pyrolysis, producing hydrogen and methane and reactions that cleave the aromatic rings and produce carbon monoxide.     

Mass spectral characteristics of poly(2,6-dimethyl-1,4-phenylene ether)

The mass spectral characteristics of poly(2,6-dimethyl-1,4-phenylene ether), its monomer (2,6-xylenol), and its dimer (3,5-dimethyl-4-hydroxyphenyl 2,6-xylyl ether) have been determined. The monomer and dimer show peaks for the molecular ions (122; 242 amu) and degradation patterns similar to those of o-methylaryl ethers. Loss of methyl and cleavage of the ether with transfer of an o-methyl hydrogen are observed. Metastable transitions are recorded corresponding to a loss of 15 from 122 and 56 from 107 amu (xylenol) and of 151 from 242 and 40 from 104 amu (ether). The polymer volatilizes readily at 380–400°C. (TGA shows rapid weight loss at 400°C) and gives sets of peaks at (N × 120) ± 14 up to 1080 (N = 9). The principal peak is at (N × 120) + 2, calibrated against PFA, and this is attributed to an ion of a volatilized oligomer. The oligomer is either present as such, is formed in a degradation process involving an ether redistribution, or is formed in a hydrogen transfer process in the ether cleavage reaction.     

The thermal properties of poly(oxy-1,4-benzoyl), poly(oxy-2,6-naphthoyl), and its copolymers

The thermal properties, i.e., heat capacity, enthalpy, entropy, and Gibbs function, and the transition behavior of the copolymer system of 4-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid have been studied based on differential scanning calorimetry. The heat capacities of the glass, crystal, and anisotropic melt are shown to be largely additive on a molar basis. Additivity is lost in the two transition regions, glass transition and disordering transition. Isothermal crystallization experiments on the copolymers revealed the existence of two types of crystals which melt at high temperature (fast-grown crystals) and low temperature (slowly grown crystals). The ATHAS computation method is used to bring heat capacities of the solid state into agreement with approximate frequency spectra. The changes in heat capacity at the glass transitions occur at 434°K for the poly(oxy-1,4-benzoyl) [33.2 J/(K mol)] and at 420°K for poly(oxy-2,6-naphthoyl) [46.5 J/(K mol)]. The copolymers have a transition range of above 100°K. The anisotropic melt is linked to the well-known condis state of poly(oxy-1,4-benzoyl) by a continuous changes in disorder and mobility without an additional first-order transition.     

Chemical modification of poly(2,6-dimethyl-1,4-phenylene oxide) by bromination-alkynylation

The chemical modification of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) by bromination of the aromatic ring, followed by displacement of bromine with substituted acetylenes, has been investigated. This pathway leads to a series of novel copolymers containing substituted alkynes on the aromatic ring. The degree of bromination and alkynylation, determined by ¹H-NMR, was in the range of 20–85 and 15–80%, respectively. ¹³C-NMR and FT-IR unambiguously elucidated the structure of the alkynylated polymers. Finally, thermal properties and permeation properties of substituted PPO to carbon dioxide, methane, oxygen, and nitrogen are reported. © 1994 John Wiley & Sons, Inc.     

Depolymerization of poly(2,6-dimethyl-1,4-phenylene oxide) under oxidative conditions

Depolymerization of an engineering plastic, poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), was accomplished by using 2,6-dimethylphenol (DMP) under oxidative conditions. The addition of an excess amount of DMP to a solution of PPO in the presence of a CuCl/pyridine catalyst yielded oligomeric products. When PPO (M(n)=1.0x10(4), M(w)/M(n)=1.2) was allowed to react with a sufficient amount of DMP, the molecular weight of the product decreased to M(n)=4.9x10(2) (M(w)/M(n)=1.5). By a prolonged reaction with the oxidant, the oligomeric product was repolymerized to produce PPO essentially identical to the starting material, making the oligomer useful as a reusable resource. During the depolymerization reaction, an intermediate phenoxyl radical was observed by ESR spectroscopy. Kinetic analysis showed that the rate of the oxidation of PPO was about 10 times higher than that of DMP. These results show that a monomeric phenoxyl radical attacks the polymeric phenoxyl to induce the redistribution via a quinone ketal intermediate, leading to the substantial decrease in the molecular weight of PPO, which is much faster than the chain growth.     

Anionic graft polymerization of lithiated poly(2,6-dimethyl-1,4-phenylene ether)

Lithiated poly(2,6-dimethyl-1,4-phenylene ether) has been used as an initiator for the graft polymerization of isoprene, methyl methacrylate, hexamethylcyclotrisiloxane, and phenyl isocyanate with the use of toluene and tetrahydrofuran as solvents. The products were examined by gel-permeation chromatography for evidence of homopolymerization and graft polymerization. The composition of the graft copolymers was determined by NMR, and for isoprene and hexamethylcyclotrisiloxane, termination by trialkylchlorosilanes enabled chain lengths to be determined by NMR. The use of toluene gave rise to some homopolymerization, but with tetrahydrofuran, only hexamethylcyclotrisiloxane gave homopolymer. In all cases, graft copolymers were formed. With isoprene and methyl methacrylate, soluble graft copolymers were formed in good yield. In the former case approximately 60% 3,4 and 40% 1,4 addition was found. In the latter case 1,1-diphenylethylene was used to reduce crosslinking, in its absence, methyl methacrylate gave only crosslinked gels in tetrahydrofuran. Hexamethylcyclotrisiloxane added only one molecule per lithium on the polymer, the remainder giving homopolymer. Phenyl isocyanate gave some soluble graft copolymer in toluene, but only crosslinked products were obtained when tetrahydrofuran was used as reaction solvent.     

Thermal degradation and stabilization of poly(2,6-dimethyl-1,4-phenylene oxide)

Thermal degradation and stabilization of poly(2,6-dimethyl-1,4-phenylene oxide) have been examined in air in the range 100–400°. Plots of weight-average molecular weight vs time are linear, confirming random chain scission. The breakdown process has also been studied by DTA and TGA. It was concluded that thermal analysis alone was insufficient to characterize the degradation fully so the degradation products were determined qualitatively using i.r. and NMR spectroscopy. The heats of activation for the systems have been calculated and a stabilization mechanism by bis(1-phenyl-3-α-pyridyl triazeno)Cu(II) chelate has been postulated.