Stress-induced structure transition of syndiotactic polypropylene via melt spinning

Syndiotactic polypropylene (sPP) fiber was prepared by melt spinning with the taken-up velocity of 200-700 m/min, the conformation and crystallization of which were systematically investigated by a combination of Fourier transform infrared (FTIR) spectroscopy, wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The results indicated that sPP fibers consist of form I crystal with helical conformation at the spinning velocity of 200-300 m/min, and the crystallinity and orientation are improved with the increase of spinning velocity in this range. As the spinning velocity exceeds 300 m/min, sPP fibers contain mainly mesophase with trans-planar conformation and the content of form I decreases correspondingly. The crystallization behavior of sPP fiber with spinning velocity is different from that of most other crystalline polymers, i.e., the theory of orientation-induced crystallization is not well conformed to. For sPP, form I comprising of helical conformation is thermodynamically stable, though extensional stress can lead to transition from helical to trans-planar conformation, which is not favorable for the crystallization of form I.     

Effect of gas pressure on the phase behaviour of organometallic compounds

The knowledge of the phase behaviour of organometallic compounds in supercritical CO₂ is the key factor for determining the feasibility of homogeneous catalysis in supercritical fluid reaction. In the present study, the solid-liquid-gas equilibrium line for the system CO₂/Cu(thd)₂, CO₂/Pt(COD)Me₂ and He/Pt(COD)Me₂ was determined from 0.1 MPa to 25 MPa. In addition, experimental solubility data of Cu(thd)₂ in CO₂ at 333 K and pressures ranging from 10 MPa to 17 MPa as well as of Pt(COD)Me₂ in CO2 at 313 K, 333 K and 353 K and pressures ranging from 12 MPa to 32 MPa are presented. The solubility data are correlated using the linear relationship between the logarithm of the solubility and the logarithm of the reduced density of pure CO₂ proposed by Kumar and Johnston as well as an extension of the theory of dilute solution proposed by Mendez-Santiago and Teja. Both approaches gave reasonable results in the correlation of the experimental solubility data.     

Interfacial tension of linear and branched PP in supercritical carbon dioxide

In this study, sessile drops are imaged in a high-pressure and high-temperature view chamber to determine the density and interfacial tension of linear polypropylene (LPP) and branched polypropylene (BPP) melts in supercritical carbon dioxide (CO₂). The pressure-volume-temperature (PVT) data of polyprophylene (PP)-CO₂ is investigated by monitoring the swelling changes of the polymer melt in supercritical CO₂. The density difference between the polymer/CO₂ mixture and the CO₂ is determined by combining the swelling results with the CO₂ solubility information in the polymer melt. Both the Sanchez-Lacombe (SL) and the Simha-Somcynsky (SS) equations-of-state (EOS) are applied to predict the density of the PP-CO₂ mixture, which is then compared to the density data obtained experimentally. The dependence of interfacial tension on the temperature and pressure of PP in supercritical CO₂ is investigated at temperatures from 180 °C to 220 °C and pressures up to 31 MPa. Effects of long-chain branching on the density and interfacial tension of PP-CO₂ mixtures are discussed.     

Morphological changes in poly(?-caprolactone) in dense carbon dioxide

Morphological changes that take place in poly(?-caprolactone) upon exposure to carbon dioxide at high pressures have been explored as a function of pressure and temperature. SEM and DSC results point to a competition between CO₂-modulated crystallization and pressure-induced phase separation which leads to unique morphologies. At 293 K, exposure to CO₂ at pressures up to 45 MPa leads to recrystallization resulting in higher level of crystallinity and higher melting temperatures. Highest crystallinity levels along with distinct crystal morphology were observed after exposure to CO₂ at 308 K and 21 MPa. At a higher pressure at this temperature (308 K/34 MPa) polymer undergoes melting, and foaming is achieved during depressurization prior to solidification. At 323 K, the polymer is found to display unique crystal morphology with concave crystal geometry as well as porous domains. The results are discussed in terms of the crystallization and phase separation paths that are followed during exposure to CO₂ and the depressurization stages.     

Structure of syndiotactic propylene-ethylene copolymers: Effect of the presence of ethylene units on the structural transitions during plastic deformation and annealing of syndiotactic polypropylene

Syndiotactic propylene-ethylene copolymers have been synthesized with a single-center C_s-symmetric syndiospecific metallocene catalyst. A study of the effect of the presence of ethylene comonomeric units on the polymorphic behavior of syndiotactic polypropylene (sPP) and on the structural transitions occurring during stretching is reported. For copolymer samples with low ethylene contents, in the range 2-7 mol%, crystals of the helical form I, present in the melt-crystallized samples, transform into the trans-planar form III by stretching at high deformation. Form III transforms in part into the helical form II by releasing the tension, as it occurs for sPP. Samples with ethylene contents in the range 8-10 mol% are crystallized from the melt as a mixture of crystals of helical form I and form II. Both helical forms transform by stretching at low values of deformation (lower than 300%) into the trans-planar mesomorphic form, which transforms into the trans-planar form III by further stretching at higher deformations (higher than 500%). For these samples form III transforms back into the mesomorphic form, rather than into the helical forms, by releasing the tension. Unoriented samples of copolymers with ethylene content in the range 13-18 mol% are mainly crystallized in the helical form II, which transforms into the trans-planar mesomorphic form by stretching. Upon releasing the tension the mesomorphic form remains stable and no polymorphic transition is observed. The presence of ethylene comonomeric units stabilizes the trans-planar forms in fibers of the copolymer samples. This has been confirmed by the result that for high ethylene contents the trans-planar form III and the mesomorphic form do not transform in helical forms by annealing of fibers stretched at high deformations.     

Supercritical carbon dioxide‐induced melting temperature depression and crystallization of syndiotactic polypropylene

This work was aimed at studying supercritical carbon dioxide (scCO₂)‐induced melting temperature depression and crystallization of a syndiotactic polypropylene (sPP). Under scCO₂, the melting temperature of the sPP could be significantly reduced depending on the CO₂ pressure. The scCO₂‐induced crystallization of sPP was investigated using differential scanning calorimeter (DSC) and Fourier transform infrared spectroscopy. Two melting peaks were observed in DSC. The one at lower melting temperature referred to the melting of the sPP crystals induced by scCO₂ in its amorphous phase. Its location was shifted to higher temperature, and its area increased with increasing scCO₂ treatment time, temperature, and pressure. The melting peak at higher temperature corresponded to the melting of the sPP crystals that already existed before scCO₂ treatment. Its location and area remained almost unaffected by the scCO₂ treatment. The scCO₂‐induced crystallization was related to scCO₂‐promoted transformation of the mesophase form III of the sPP to the stable form I. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Direct melt-crystallization of isotactic poly-1-butene with form I′ using high-pressure CO2

In this work, we found a new method to obtain isotactic poly-1-butene (iPB-1) with form I′ through direct melt-crystallization using high-pressure CO₂. The non-isothermal melt-crystallization behaviors of iPB-1 under atmospheric N₂ and 0.5-10 MPa CO₂ at cooling rates ranging from 0.25 to 5 °C/min were carefully studied using high-pressure differential scanning calorimeter (DSC) and analyzed using the modified Avrami method. Wide-angle X-ray diffraction (WAXD) measurements showed that the crystal structure of non-isothermally melt-crystallized iPB-1 changed from form II under atmospheric N₂ and 0.5-8 MPa CO₂ to form I′ under 10 MPa CO₂. In-situ high-pressure Fourier transform infrared (FTIR) was also used to investigate the non-isothermal melt-crystallization at CO₂ pressure up to 18 MPa at the cooling rate of 1 °C/min. Likewise, it was found that form II crystallized under atmospheric N₂ and 0.5-8 MPa CO₂, and form I′ melt-crystallized directly at CO₂ pressures higher than 10 MPa, which was confirmed by the followed DSC and WAXD characterizations on the iPB-1 films after FTIR measurements. The crystal morphology of the melt-crystallized iPB-1 films, characterized by using polarized optical microscopy (POM), showed that the Maltese cross pattern of iPB-1 spherulite became more diffuse with increasing CO₂ pressure, and the spherulite size decreased abruptly at the CO₂ pressure of 10 MPa.     

Observation of liquid solution volume expansion during particle precipitation in the supercritical CO2 antisolvent process

An optical measurement technique, which is based on the Foerster resonant energy transfer (FRET) between two different dye molecules, has been applied successfully to observe volume expansion of a liquid solution, when it is pressurized with CO₂. Rhodamine-B and Rhodamine-700 were dissolved in ethanol to form the FRET active dye solution. In a first “prove of principle” experiment, the sensitivity of the FRET efficiency towards volume expansion was demonstrated by pressurizing the liquid dye solution in a cuvette with CO₂. From the rise of the meniscus of the solution inside the cuvette as a function of CO₂ pressure, the simultaneously acquired FRET spectra could be correlated with the volume expansion of the dye solution. In a second experiment, the dye solution was injected into CO₂ at different supercritical antisolvent operation pressures. FRET spectra were recorded 3 mm downstream of the injector nozzle, always upstream of the breakup of the injected liquid solution. At pressures below the thermodynamic mixture critical pressure (7.9 MPa @ 313 K) of the system ethanol/CO₂ no liquid phase volume expansion was observed. At pressures between the thermodynamic and the dynamic mixture critical pressure (8.5 MPa @ 313 K) of the same system, volume expansion could be evidenced before the breakup of the injected liquid solution.     

Theoretical study on interaction between CO2 and carbonyl compounds: Influence of CO2 on infrared spectroscopy and activity of CO

The interactions between CO₂ and carbonyl compounds at different CO₂ pressures have been studied both experimentally and theoretically. In situ high-pressure FTIR on carbonyl compounds, i.e., acetaldehyde, acetone, and crotonaldehyde, in supercritical CO₂ have been measured at various CO₂ pressures varying from 6 to 22 MPa. In order to get insights into the mechanism, theoretical study has been conducted concerning the effect of CO₂ on frequency shift of CO in acetaldehyde, acetone, benzaldehyde, crotonaldehyde and cinnamaldehyde at different CO₂ pressures. It has been shown that the experimental frequency shifts can be well simulated by the theoretical model calculations using particular structures, in which a carbonyl compound interacts with a few CO₂ molecules, depending on the carbonyl compounds examined, except for acetaldehyde.The interaction energies between CO₂ and those carbonyl compounds are also given. In addition, the effect of CO₂ on hydrogenation of crotonaldehyde and benzaldehyde has been discussed by means of the local softness (s⁺) calculated at CO₂ pressures of 0-22 MPa, which can explain the reactivity difference in the crotonaldehyde and benzaldehyde hydrogenations in supercritical CO₂.     

Extraction of sage (Salvia officinalis L.) by supercritical CO2: Kinetic data, chemical composition and selectivity of diterpenes

The supercritical carbon dioxide (SFE) extraction of Dalmatian sage (Salvia officinalis L.) was investigated and compared to extraction performed by Soxhlet ethanol-water (70:30) mixture extraction (SE) and hydrodistillation (HD). The supercritical extraction allowed isolation of wide spectrum of phytochemicals, while other applied methods were limited to either volatiles (HD) or high molecular compounds isolation (SE). The kinetics of the supercritical extraction and fractionation within the pressure range of 10-30 MPa at 50 °C were also analyzed as well as the chemical compositions of total extract and partial or differential fractions isolated at different CO₂ consumption. Volatile fraction could be isolated at low pressure and low CO₂ consumption, whereby the pressures between 10 and 15 MPa followed by increased CO₂ consumption were favourable for obtaining desired selectivity of diterpenes which contain compounds with expressed antioxidative characteristics.     

Partitioning of drug model compounds between poly(lactic acid)s and supercritical CO2 using quartz crystal microbalance as an in situ detector

Quartz crystal microbalance (QCM) was used as an in situ detector to investigate the potential application in the phase equilibrium determination of supercritical CO₂-drug-polymer systems. CO₂ solubility in two biodegradable polymers, poly(d,l-lactic acid) (d,l-PLA) and poly(l-lactic acid) (l-PLA) was primarily measured at 313.15 K and pressures up to 10.0 MPa. d,l-PLA showed a better CO₂ absorption ability due to its amorphous structure. Four drug model compounds of poor solubility in water, ibuprofen, aspirin, salicylic acid and naphthalene were selected as representatives for the examination of drug uptake in PLA matrices, as well as partition coefficient during supercritical impregnation. It was found that partition coefficients of drugs can reach as high as 10³-10⁴ orders of magnitude and greatly affected by the intermolecular interactions between drugs and PLA. Aspirin exhibited the best partitioning during the supercritical impregnation at pressures of 8.0-10.0 MPa due to the existence of carboxylic acid and acetyl groups. Drug partitioning is additionally related to the drug concentration in ScCO₂, i.e. salicylic acid showed little absorption in PLA according to its poor solubility in ScCO₂ at 7.5-8.0 MPa, whereas the well CO₂-soluble compound, naphthalene, exhibited a moderate partition coefficient although its polarity was different from l-PLA.     

Melt compounding of syndiotactic polypropylene nanocomposites containing organophilic layered silicates and in situ formed core/shell nanoparticles

Syndiotactic polypropylene (sPP) compounds containing organophilic layered silicates were prepared by means of melt extrusion at 220 °C using a corotating twin screw extruder in order to examine the influence of the silicate modification and the addition of maleic-anhydride-grafted isotactic polypropylene (iPP-g-MA) as compatibilizer on morphology development and mechanical properties. Synthetic sodium fluoromica was used as water-swellable layered silicate, which was rendered organophilic by means of cation exchange with protonated octadecylamine. Only compounding of the modified silicate in conjunction with iPP-g-MA afforded exfoliation and dispersion of individual silicate layers, encapsulated in an iPP-g-MA shell, within the polypropylene matrix. Interlayer distance increased with increasing content and increasing molecular weight of the compatibilizer. The Young's modulus of the nanocomposite increased fivefold from 490 to 2640 MPa. This was attributed to silicate nanoreinforcement and nucleation of sPP crystallization via the iPP-g-MA shell of the dispersed organophilic silicate nanoparticles. The yield stress was increased to 29 MPa with respect to 16 MPa for the bulk sPP. Morphology and mechanical properties were examined as a function of the silicate—and compatibilizer content.     

Equilibrium solubilities of a p-toluenesulfonamide and sulfanilamide mixture in supercritical carbon dioxide with and without ethanol

Supercritical separation processes for a multi-component mixture of solutes are of practical interest. In this study, the experimental equilibrium solubilities of two solute mixtures, p-toluenesulfonamide (p-TSA) and sulfanilamide (SNA), in supercritical carbon dioxide (SC CO₂) were measured at temperatures of 308, 318 and 328 K and pressures in the range of 11.0-21.0 MPa using a dynamic flow method. The effect of cosolvent on the multi-component system was investigated by the addition of a 3.5 mol% ethanol. In the ternary system (p-TSA + SNA + CO₂), the solubility of SNA increased as compared to its binary system (SNA + CO₂), while the solubility of p-TSA decreased. In the quaternary system (p-TSA + SNA + ethanol + CO₂), a significant solubility enhancement was observed for both p-TSA and SNA. The selectivity, which is thought to imply the intermolecular interactions between p-TSA and SNA, was also enhanced by the presence of ethanol so that the two solutes could be separated by a max. purity of 99.4%. The influence of the hydrogen bond interaction on solubility was discussed. The equations of Chrastil, Méndez-Santiago and Teja, and their modified forms were used to correlate the experimental data.     

Supercritical CO2 extraction of Helichrysum italicum: Influence of CO2 density and moisture content of plant material

Kinetics and selectivity of supercritical carbon dioxide (SC CO₂) extraction of Helichrysum italicum flowers were analyzed at pressures in the range of 10-20 MPa and temperatures of 40 °C and 60 °C (density of SC CO₂ from 290 to 841 kg/m³) and also at 10 MPa and 40 °C using flowers with different moisture contents (10.5% and 28.4%). Increased moisture content of H. italicum flowers resulted in enchased solubility of solute enabling decrease of SC CO₂ consumption necessary for achieving desired extraction yield. The most abundant compounds in the supercritical extracts are sesquiterpenes and waxes while monoterpenes and sesquiterpenes are the main constituents of essential oil obtained by hydrodistillation. The optimal set of working parameters with respect to extraction yield, SC CO₂ consumption and chemical composition of extract were defined related to moisture content of raw material and SC CO₂ density.     

Oriented crystallization in fiber formation: Inferences from the structure and properties of melt spun syndiotactic polypropylene filaments

In processes, such as melt spinning, the crystallization behavior of syndiotactic polypropylene (sPP) is found to be substantially different from that of most other linear polymers. The anisotropic stress field in such processes leads invariably to extension as well as alignment (orientation) of the chains in the melt, both of which contribute usually to dramatic enhancement in the rate of crystallization. However, since the primary structure of the sPP chain in its most preferred crystal form is comprised of a “coiled helical,” ? (T₂G₂)₂? , sequence, stress‐induced chain extension can lead to conformational sequences that are not favorable for crystallization in this form. As a consequence, process conditions that generate higher stress levels can cause a diminution in the rate of crystallization of this polymer. Such conformation‐related aspects of oriented crystallization of sPP have been addressed through an analysis of the structure and properties of melt‐spun fibers, produced over a range of spinning speeds. The results serve to identify a refinement that is needed in current models of oriented crystallization and also a mechanism to promote the nucleation of crystallization of sPP. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2305–2317, 2001     

Viscosity measurement and modeling of canola oil and its blend with canola stearin in equilibrium with high pressure carbon dioxide

During enzymatic reactions carried out in supercritical CO₂ (SCCO₂) media, CO₂ can expand the liquid reactant mixture, especially lipid-type substances, due to pressure increase and dissolution of CO₂, causing viscosity reduction, and improvement of the diffusion of reactants and products. For better understanding of the transesterification reaction of canola oil and canola stearin in SCCO₂ media, the viscosity of canola oil at 40, 50, 65, and 75 °C and its blend with canola stearin (30 wt%) at 65 °C in equilibrium with high pressure CO₂ was measured up to 12.4 MPa using a rotational rheometer equipped with a high pressure cell. The solubility of CO₂ in canola oil at 40 and 65 °C and its blend with canola stearin at 65 °C was also determined at pressures of up to 20 MPa using a high pressure view cell. The viscosity of canola oil at 40, 50, 65, and 75 °C and its blend with canola stearin at 65 °C decreased exponentially to 87.2, 84.7, 74.8, 66.2, and 74.2% of its value at atmospheric pressure, respectively, with pressure increase up to 12.4 MPa. The viscosity of the samples decreased with an increase in temperature, but the effect of temperature diminished above 10 MPa. The viscosities of CO₂-expanded canola oil and its blend with canola stearin at 65 °C were similar up to 12.4 MPa. The samples exhibited shear-thickening behavior as the flow behavior index reached almost 1.2 at elevated pressures. The mass fraction of CO₂ in canola oil at 40 and 65 °C and its blend with canola stearin at 65 °C reached 24 and 21% at 20 MPa, respectively. The Grunberg and Nissan model was used to correlate the viscosity of CO₂-expanded lipid samples.     

CO2-induced polymorphous phase transition of isotactic poly-1-butene with form III upon annealing

In-situ high-pressure FTIR was used to investigate the polymorphous phase transition of isotactic poly-1-butene (iPB-1) with form III upon annealing at temperatures ranging from 75 to 100 °C and CO₂ pressures ranging from 2 to 12 MPa. It was shown that the phase transition of form III changed from form III to II not through form III to I′ with increasing temperature and application of CO₂ increased the content of generated form I′. Wide-angle X-ray diffraction (WAXD) measurement on the annealed iPB-1 with form III verified the phase transition of form III. The crystalline morphology of the annealed iPB-1 films was investigated using polarized optical microscopy (POM). The results implied that the phase transition of form III to I′ might process via a solid-solid transition, which did not affect the orientation of the lamellar stacks. The orientation of form II lamellar stacks depended strongly on the formation process. To obtain strong orientation, the formation process displayed the following order: melt crystallization at ambient condition > melt recrystallization under CO₂ > phase transition upon annealing at ambient condition. Avrami equation could be well established to describe the phase transition of form III to I′ through a solid-solid phase transition.     

Impregnation of vitamin E acetate on silica mesoporous phases using supercritical carbon dioxide

Impregnation of a drug model (α-tocopheryl acetate) into mesoporous host matrices has been carried out using supercritical carbon dioxide (SC CO₂) as impregnation solvent at 15 MPa and 313 K with a flow rate of 500 g h⁻¹. The operating conditions were defined following the solute concentration in the fluid phase as a function of pressure and carbon dioxide flow rate. Solubility measurements of α-tocopheryl acetate were first performed at 313 K for pressures ranging 10-20 MPa. High values of solubility in SC CO₂ were measured: 6 wt% at 10 MPa and 14 wt% at 20 MPa. Measurements of the concentration of the solute in SC CO₂ in the experimental conditions of impregnation in dynamic mode showed than it was ten times lower than the solubility. The variations of this concentration have been studied at 313 K, for a pressure varying from 8 to 15 MPa, and for a carbon dioxide flow rate varying from 120 to 600 g h⁻¹. Two different host matrices were used: a commercial chromatographic silica support and a MCM-41-type mesoporous organized silica synthetized at the laboratory. This latter showed the best drug loading of 1.14 g per gram of adsorbent. The drug loadings obtained in supercritical media were similar to the ones obtained in liquid media using hexane as impregnation solvent. Nevertheless, the maximum loading was obtained after 1 h of impregnation in SC media while 4 h were needed in liquid media.     

Nonisothermal melt crystallization kinetics of syndiotactic polypropylene/alumina nanocomposites

Nonisothermal melt crystallization kinetics of syndiotactic polypropylene (sPP)/alumina nanocomposites were investigated via differential scanning calorimetry. The addition of alumina nanoparticles significantly increases the number of nuclei and promotes the crystallization rate of sPP. Nonisothermal melt crystallization kinetics was analyzed by fitting the experimental data to a Nakamura model using Matlab. The average values of Avrami exponent n are 1.7 for both sPP and sPP/Al₂O₃ nanocomposites during slow cooling, which implies a two‐dimensional growth is the predominant mechanism of crystallization following a heterogeneous nucleation. The two nanocomposites give n values equal to 2.3 during faster cooling, indicating that the main growth type taking place for sPP/alumina nanocomposites is also the two‐dimensional growth. The subsequent melting behavior shows that the presence of alumina nanoparticles changed both the cold crystallization and the recrystallization of sPP. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Processing triacetyl-β-cyclodextrin in the liquid phase using supercritical CO2

TA-β-CD has been proposed as an effective sustained release carrier for highly water soluble drugs with short biological half-lives. In this work, the possibility of preparing drug - triacetyl-β-cyclodextrin (TA-β-CD) complexes in the liquid phase by exploring its solid-liquid-gas equilibrium (S-L-G) under supercritical CO₂ atmosphere was evaluated. The S-L-G equilibrium line for the binary system TA-β-CD + CO₂ was determined by a visual method for pressures up to 25.3 MPa. At the studied conditions, a homogeneous and translucent liquid phase emerge at 307 K when exposed to CO₂ pressurized at 16 MPa and this temperature further increases with increasing pressure, up to 318 K at 25.3 MPa. The S-L-G equilibrium behaviour observed is typical of this kind of asymmetric systems, it is totally CO₂ density-dependent and opens the possibility of further processing TA-β-CD in the liquid phase. In order to investigate the possibility of preparing a drug-TA-β-CD complex in the liquid phase of TA-β-CD, a preliminary experiment was performed at 25 MPa and 308 K using flufenamic acid (FA) as the model active principle.