A differential scanning calorimeter study of the crystal forms and polymerization kinetics of 2,4-hexadiynyl-1,6-bis(p-toluenesulfonate)

The thermal properties of 2,4-hexadiynyl-1,6-bis(p-toluenesulfonate) have been explored by program temperature and isothermal differential calorimetry. The heat of fusion for the rapidly heated pure solid was 8254 cal/mole (34,540 J/mole) at 367.1°K (93.8°C). This amounts to an entropy change of 22.5 cal/mole °K (94.1 J/mole °K). The energy of activation for the thermal polymerizations was 18.97 kcal/mole (79.37 kJ/mole). The thermal polymerization appears to follow a solid–solid phase transition which proceeds by random homogeneous nucleation throughout the process. The kinetics were simple first order over 70% of the reaction. Programmed temperature studies indicate that during the first 10% of the polymerization a new high temperature (mp 375.4°K) solid phase is formed which acts as the monomer form during the bulk of the reaction.     

Radiation-induced,solid-state polymerization of derivatives of methacrylic acid. I. Postirradiation polymerization of zinc methacrylate

The postirradiation polymerization of the crystalline, anhydrous, monohydrate, and dihydrate forms of zinc methacrylate was studied. The anhydrous salt polymerized readily in the temperature range 50–150°C., the monohydrate did not polymerize at all, and the dihydrate polymerized at about 100°C. Aging of the anhydrous salts greatly affected the rate of polymerization; this was shown to be due mainly to the formation of peroxides by reaction with air. Polymerization could be initiated thermally, without irradiation, in monomer which had been aged in contact with air, apparently by decomposition of the peroxides. The rate of the postirradiation polymerization was increased when air was present during irradiation and decreased when air was present during polymerization. The rate of polymerization increased with temperature, corresponding to an apparent activation energy of 10 kcal./mole. The dihydrate lost one molecule of water rapidly under vacuum at 20°C. and slowly on heating at 50°C. in a sealed vessel, forming a crystalline monohydrate. Slow thermal polymerization and rapid postirradiation polymerization occurred at 100°C. without the formation of any monohydrate, indicating that the polymerization was concurrent with the phase change.     

Tetrachlorobisphenol-A adipate polymers. I. Crystallization of poly(tetrachlorobisphenol-A adipate)

The properties of melt-crystallized poly(tetrachlorobisphenol-A adipate) were studied by using a differential scanning calorimeter. The dependence of melting point and the degree of crystallinity are reported as a function of the crystallization conditions. The heat of fusion is equal to 8.1 kcal/mole, while the equilibrium melting point, as determined by extrapolation, is 283°C. The polymer crystallized from the melt has a maximum degree of crystallinity of 0.53.     

The synthesis and thermal polymerization of 4,4′-diethynylphenyl ether

Diethynylphenyl ether (DEPE) was synthesized and its thermal polymerization studied by NMR, IR, and DSC techniques. DEPE is a crystalline solid that melts at 72–73°C and undergoes polymerization beginning at about 150°C. The heat of polymerization measured by DSC was 53 ± 2 kcal/mole. Thermomechanical analysis (TMA) of the fully cured resin showed softening behavior at temperatures in excess of 400°C. Weight loss up to 720°C was only 21%. A mechanism of polymerization based on the analysis of IR and NMR data for party polymerized material below 300°C is proposed.     

Novel copolyesters containing naphthalene structure. II. Copolyesters prepared from 2,6-dimethyl naphthalate, 1,4-dimethyl terephthalate,and ethylene glycol

Copolyesters containing rigid segments (naphthalene and terephthalene) and flexible seg-ments (aliphatic diol) structure were synthesized from DMN/DMT/EG (2,6-dimethyl naphthalate/1,4-dimethyl terephthalate/ethylene glycol) ternary monomers with various mole ratios. Copolyesters having intrinsic viscosities of 0.52–0.65 dL/g were obtained by melt polycondensation in the presence of metallic catalysts. The effect of reaction tem-perature and time on the formation of the copolyesters was investigated to obtain an op-timum condition for copolyester manufacturing. The optimum condition for PNT (poly-ethylene naphthalate terephthalate) copolyester manufacturing is the transesterification under nitrogen atmosphere for 4 h at a temperature of 185±2°C followed by polymerization under 2 mm Hg for 2 h at a temperature of 280°C. Most copolyesters have better solubilities than poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) in various solvents. The effect of the starting mole ratio of DMN, DMT, and EG on the thermal properties of the resulted copolyesters was also investigated using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Glass transition temperatures of copolyesters were in the range of 70.7–115.2°C, and 10% weight loss in nitrogen were all above 426°C. © 1995 John Wiley & Sons, Inc.     

Crystallization during polymerization of poly-p-xylylene. II. Polymerization at low temperature

The polymerization of p-xylylene was followed with a newly designed differential thermal analysis system at temperatures between ?196°C and ?20°C. It was found that at the lower temperatures the monomer condenses first to the crystalline monomer before simultaneous polymerization and crystallization. At the higher temperatures, polymerization and crystallization are successive. The data are in agreement with the morphology and crystal structure data derived in Part I of this series of papers on crystallization during polymerization of poly-p-xylylene.     

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.     

Studies of Some Newer Polyhydrazides Containing Amide Linkages. Part 1

An attempt has been made to prepare some new polyamide hydrazides of high thermal stability with different dicarboxylic acid chlorides by the solution polymerization technique. The polymerization was carried out at -20°C. Amide linkage was present in each polymer unit. Results of thermal degradation and thermogravimetric analysis indicate that these polymers melt or decompose above 350°C, and the steep weight loss of the polymer takes place in the range 360–390°C. Most of the polyhydrazides are soluble in organic solvents.     

Direct condensation polymerization of lactic acid

In order to synthesize the higher molecular weight poly(lactic acids) by direct condensation polymerization of lactic acid, dipentaerythritol was used as a chain branching agent. Poly(lactic acids) of high molecular weight, 67000(Mn), was obtained by using antimony trioxide catalyst with good color. This poly(lactic acids) showed Tg of 54.8 °C, Tm of 147 °C and cold crystallization temperature of 115 °C. The polymer could be melt processed into transparent films. Tensile modulus of 311 Kg/ mm², tensile strain of 21% and tensile strength of 12.41 Kg/ mm² were obtained for film collected at 400%/min and drawn 4 times.     

Phase diagram for the ternary system LiClCaCl2CaCrO4

The phase diagram for the system LiClCaCl₂CaCrO₄ has been studied using differential thermal analysis. LiClCaCl₂CaCrO₄ has been shown by X-ray diffraction to be a stable, diagonal section of the Li, Ca//Cl, CrO₄ reciprocal ternary system. The three binary systems are: LiClCaCl₂ which exhibits a double salt (LiCaCl₃), which decomposes without melting at 439°C and a eutectic at 36.3 mole % CaCl₂ (m.p. 487°C); CaCl₂CaCrO₄ which shows a eutectic at 23.4 mole % CaCrO₄ (m.p. 660°C); and LiClCaCrO₄ with a eutectic at 14.3 mole % CaCrO₄ (m.p. 538°C).In the ternary system, a eutectic exists at 63.2 mole % LiCl32.9% CaCl₂3.9% CaCrO₄ (m.p. 479°C). In addition, a four-phase equilibrium, involving all solid phases, exists at nearly all compositions at 435°C.Isotherms are shown for the liquidus surface (primary crystallization) and for the secondary crystallization surface. Isothermal and vertical sections through the ternary phase diagram are shown.     

Radiation-induced ionic polymerization of isobutyl vinyl ether in bulk

The radiation-induced ionic polymerization of isobutyl vinyl ether was investigated under conditions where the monomer was dried with molecular sieves. The investigation covered the temperature range from ?16°C to 90°C, and the dose-rate range from 10¹⁵ to 10²⁰ eV/g-sec, using both γ-rays and electrons. A very high overall activation energy of 15.9 kcal/mole was found for the process below 30°C. Above 30°C, however, the value of the overall activation energy dropped to 4.9 kcal/mole, a phenomenon which is ascribed to the solvation of the propagating carbonium ion below 30°C. The dose-rate dependence of the rate of polymerization was found to be 0.58 over the entire dose-rate range investigated. The molecular weight of the polymer was found to be far less sensitive to trace amounts of water than the rate of polymerization. The molecular weight of the polymer depended strongly on the irradiation temperature, reaching a maximum value of about 120,000 at 35°C. It is shown that at temperatures above 20°C regenerative chain transfer processes play an important role in determining the molecular weight of the polymer.     

Polymerization of vinyl compounds with heterocyclic groups. IV. Thermal polymerization of 2-vinylthiophene

2-Vinylthiophene was found to undergo thermal polymerization. With benzene as diluent, the overall rate of polymerization was proportional to the 2.5 power of monomer concentration, suggesting that the thermal initiation is a termolecular process. The following Arrhenius equation was obtained from the polymerization data for the range 55–100°C: The activation energy of the thermal initiation was estimated to be 28.2 kcal/mole, which was similar to those values obtained for styrene and 2-vinylfuran. When a dilute solution of the monomer in bromobenzene was heated in an ampoule at 151°C, a dimer, mp 82°C, was obtained in a good yield. The spectroscopic data indicated that the dimer was a Diels-Alder type adduct. The initiation of the thermal polymerization was considered to involve hydrogen abstraction by monomer from the Diels-Alder dimer, in common with the initiation of other vinylaromatic monomers.     

Copolyesters of hydroxyphenylalkanoic acids: Synthesis,properties, and in vitro degradation of poly(4‐oxybenzoate‐co‐4‐oxyphenylacetate)

Hydrolytically degradable copolyesters of the naturally occurring monomer 4‐hydroxyphenylacetic acid (HPAA) with 4‐hydroxybenzoic acid (HBA) were synthesized for the first time by the acidolysis melt polymerization of their acetoxy derivatives. The HPAA/HBA copolyesters prepared by acidolysis melt polycondensation had higher yields and molecular weights than those obtained by a one‐pot method. The high‐temperature solvent Dowtherm® improved the color of the polyester. Although catalysts did not affect the inherent viscosity and yield of the polymer, they did reduce the polymerization time. A higher degree of polymerization was achieved with postpolymerization and annealing techniques. Copolyesters prepared in different molar ratios were analyzed by elemental analysis, IR, NMR, and inherent viscosity and were further characterized for their thermal and phase properties by thermogravimetric analysis, differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized light microscopy. The composition of the copolyesters affected the yield, solubility, and inherent viscosity. The NMR data indicated comparatively high randomization for the copolyester obtained by acidolysis melt polymerization. The 60/40 HPAA/HBA copolyester formed a birefringent melt with a grainy texture above 175 °C with isotropization at 297 °C and thermal stability above 350 °C. The occurrence of birefringence with a grainy texture in the melt indicates a layered smectic phase; this was supported by wide‐angle X‐ray diffraction powder patterns. The in vitro hydrolytic degradability of the copolyester was studied by the measurement of the water absorption of the film samples in buffer solutions of pH 7 and 10 at 30 and 60 °C. The copolyester showed considerable hydrolytic degradation, enough to be called biodegradable, compared with the commercial polyester Vectra®, thereby demonstrating prospects for syntheses of copolyesters with tailor‐made degradability. The degradation of the copolyester was identified by Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy. These polyesters with controlled crystallinity and degradability should be considered for possible applications in biomedical areas (e.g., bone fixation devices in fracture treatment) in which high strength with biodegradability is an essential requirement. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 693–705, 2001     

Crystallization Behavior of Poly(3-hydroxybutyrate) (PHB), Poly(ε-caprolactone) (PCL) and Their Blend (50:50 wt.%) Studied by 2D FT-IR Correlation Spectroscopy

Variable-temperature FT-IR spectra of poly(3-hydroxybutyrate) (PHB), poly(ε-caprolactone) (PCL) and a PHB/PCL (50:50 wt.%) blend were analyzed by two-dimensional correlation spectroscopy (2DCOS). For this purpose the ν(CO) region was employed to characterize in some detail the crystallization behavior of the investigated polymer systems during cooling from the melt. The asynchronous 2D correlation spectra clearly captured the existence of three components in the crystallinity-sensitive region of the CO stretching mode for PHB and PCL, respectively: a well-ordered, an inter-mediate and a less ordered crystalline state. Furthermore, by 2DCOS application a sequential order of the observed structural changes could be proposed for the whole temperature range during the crystallization of both polymers. In the case of the PHB/PCL (50:50 wt.%) polymer blend, we have split up the spectral data set in the sub-sets between 200–120 °C and 70–30 °C for a more detailed 2DCOS analysis. In this way we could separate the crystallization process of PHB and PCL in the polymer blend.     

Synthesis and Characterization of Indium-borate Glass-ceramics Containing Ho0.01Ce0.74Zr0.25O1.995 Nanorods via Incorporation Method

Glasses in the system 5In₂O₃·94Na₂B₄O₇ were fabricated via melt quenching technique. The amorphous nature of the quenched glasses was confirmed by X‐ray powder diffraction studies, and the infrared spectra of the glasses show no boroxol ring formation in the structure of these glasses. Differential thermal analysis is shown glass transition temperature 696°C and crystallization temperature 1151°C. A cerium‐zirconium mixed oxide Ce_0.75Zr_0.25O₂ and Ho‐doped cerium‐zirconium mixed oxide were obtained by solid‐state method. Then glass powder and Ho‐doped cerium‐zirconium mixed oxide were mixed. The mixture was heated in a crucible. The glass‐ceramic sample was obtained by pouring the melts on stainless steel. Obtained samples were annealed at 450°C for 1 h to remove thermal strain. Differential thermal analysis for glass‐ceramic sample is shown glass transition temperature 668°C and crystallization temperature 1159°C. The scanning electron microscopy study for glass‐ceramic indicates that the crystallized glass consists of rod‐like crystals with average diameter of about 38 nm dispersed in the glassy regions.     

Solid-state forms of prilocaine hydrochloride

Two polymorphic forms, a dioxane solvate and the amorphous form of the local anaesthetic drug prilocaine hydrochloride (N-(2-methylphenyl)-2-propylamino monohydrochloride, PRCHC) were characterized by thermal analysis (hot stage microscopy, differential scanning calorimetry, thermogravimetry), vibrational spectroscopy (FTIR, FT-Raman-spectroscopy), powder X-ray diffractometry and water vapor sorption analysis. The formation and thermodynamic stability of the different solid phases is described and presented in a flow chart and an energy temperature diagram, respectively. Mod. I° (m.p. 169°C) is the thermodynamically stable form at room temperature and present in commercial products. This form crystallizes from all tested solvents except 1,4-dioxane which gives a solvate with half a mole of 1,4-dioxane per mole PRCHC. Mod. II occurs only on desolvation of the dioxane solvate and shows a lower melting point (165.5°C) than mod. I° and a lower heat of fusion. Thus, according to the heat of fusion rule, mod. II is the thermodynamically less stable form in the entire temperature range (monotropism) but kinetically stable for at least a year. Freeze-drying of an aqueous solution leads to the amorphous form. On heating and in moist air amorphous PRCHC exclusively crystallizes to the stable mod. I°. PRCHC exemplifies that certain metastable polymorphic forms are only accessible via a specific solvate, but not via any other crystallization path. Since no crystallization from 1,4-dioxane was performed in earlier solid-state studies of this compound, PRCHC was to this date rated as monomorphic. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and rheology of biodegradable poly(glycolic acid) prepared by melt ring‐opening polymerization of glycolide

Ring‐opening polymerization (ROP) of glycolide was studied in melt conditions and in the presence of two different initiators: 1‐dodecanol and 1,4‐butanediol and tin(II) 2‐ethylhexanoate as catalyst. Its subsequent polymerization provided poly(glycolic acid) with controlled molar masses ranging from 2000 to 42,000 g/mol with well‐defined structures characterized by NMR. Their thermal properties were evaluated by DSC analysis, and a glass transition temperature at infinite molar mass (T_g∞) of 44.8 °C was thus calculated. From rheological data, the critical molar mass for entanglement, M_c, was estimated to be near 11,000 g/mol. Furthermore, in situ polymerizations were also performed between the plates of the rheometer within a same temperature range from 210 to 235 °C. The variation of the storage and loss moduli during the polymerization step have been monitored by time sweep oscillatory experiments under an angular frequency ω = 10 rad/s. Finally, the development of an inverse rheological method allowed to calculate the bulk polymerization kinetics in the temperature range 200–230 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1440–1449, 2009     

A calorimetric investigation on high molecular weight polyethylene reactor powders

Reactor powders of high- and ultrahigh-molecular weight polyethylene have been investigated. Two different Ziegler-Natta synthesis processes were used: polymerization in a slurry and in the gas phase. Synthesis temperature range was 30–85°C. Monoclinic crystals were identified in samples synthesized at 30°C. Investigations of thermal parameters were carried out by differential scanning calorimetry. A range of heating rates (0.4–10.0°C/min) was used to obtain information on sample reorganization on heating. The corresponding melt-crystallized samples were scanned and their thermal parameters were compared with those obtained from the original nascent powders. Percent crystallinity and average lamellar thickness, computed by the Thompson-Gibbs equation, were found to be controlled by conditions of synthesis. For reactor powders, the fraction of crystallinity is found to be insensitive to synthesis temperature. Crystallinity is controlled mainly by the synthesis process type: slurry or gas phase. Lamellar thickness was found to decrease as synthesis temperature was increased. This trend is the opposite of what is obtained on melt crystallization and can be interpreted on the basis of Lauritzen and Hoffman's theory of crystal growth. Nascent reactor powders give experimental support for the dependence of lamellar thickness on crystallization temperature that follows the pattern described in the theory at high undercooling. The influence of molecular weight on crystallinity and lamellar thickness of both nascent powders and melt-crystallized samples was also studied. Catalyst and synthesis conditions were found to control crystallinity and crystallite dimensions of the reactor powders. Thus, polyethylenes suitable for a specific purpose can be obtained directly on synthesis.     

Melting and crystallization of poly(vinylidene fluride) under high pressure

Precise melting and crystallization temperatures of extended-chain and folded-chain crystals of form I and folded-chain crystals of form II poly(vinylidene fluoride) under high pressure have been obtained by microdifferential thermal analysis (DTA). Upon heating at pressures above 4000 kg/cm², the micro-DTA thermogram of form II crystallized from the melt at atmospheric pressure shows melting of the form II structure and the melting of the folded-chain and extended-chain crystals of form I, formed through recrystallization processes. These features were clarified by supplemental methods. The bandwidth seen in electron micrographs of the extended-chain crystal of form I obtained by crystallization under high pressure was in the range of 1500 to 2000 Å. At atmospheric pressure, the extended-chain crystal of form I melted at 207°C, approximately 17°C higher than the folded-chain crystal of form I and 31°C higher than the folded-chain crystal of form II.