Preparation, characterization, and supercritical carbon dioxide foaming of polystyrene/graphene oxide composites

Graphene oxide (GO) was prepared by oxidation of graphite using the Hummers method, and was modified by isocyanate to obtain dispersed GO sheets in dimethylformamide. Polystyrene (PS)/GO composites were prepared by solution blending, and their morphologies and properties were characterized. The addition of GO increased the glass transition temperature of the PS/GO composites. The storage modulus and thermal stability of the composites were also improved compared with PS. Foams of PS and PS/GO composites were prepared by supercritical carbon dioxide foaming. The composite foams exhibited slightly higher cell density and smaller cell size compared with the PS foam, indicating the GO sheets can act as heterogeneous nucleation agents.     

Preparation of molecular dispersed polymer blend composed of polyethylene and poly(vinyl acetate) by in situ polymerization of vinyl acetate using supercritical carbon dioxide

A novel polymer blend comprising polyethylene (PE) and poly(vinyl acetate) (PVAc) with a biocompatible surface was developed for fabricating medical devices. This blend was obtained by a new synthetic method using supercritical carbon dioxide fluid. Further, the acetyl group on the surface of this blend was converted to the hydroxyl group following the phosphorylcholine (PC) group. Surface analysis of the blend with attenuated total reflection Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy and dynamic contact angle measurement revealed that the PC groups were located on the surface. Biocompatibility was evaluated by the adsorption of the bovine serum albumin and bovine plasma fibrinogen on the sheet surface. The hydrophilicity of the blend depended on the surface chemical structure introduced by surface reactions. Plasma protein adsorption decreased with the surface hydrophilicity. The PC groups were highly effective in reducing protein adsorption. We conclude that our process is a promising procedure for synthesizing new polymer materials including biomaterials.     

Thermodynamics of mixing of poly(vinyl chloride) and poly(ethylene-co-vinyl acetate)

The miscibility of poly(vinyl chloride) (PVC) and an ethylene-vinyl acetate copolymer with 85 wt[percnt] of vinyl acetate units (EVA85) has been studied by measuring the glass transition temperature and the enthalpy of mixing of several mixtures covering the whole composition range. An accurate thermal characterization as regards the specific heat of the two polymers and their blends has also been obtained. The enthalpy of mixing has been found negative for all the mixtures, indicating that specific interactions are involved between the polar groups of the two components. Particular attention has been paid also to the excess specific heat, which comes out positive for the PVC-rich blends and with a small negative value in a narrow region at high contents of EVA85. This finding is in agreement with negative and positive deviations that are observed for the glass transition temperature. Modelistic considerations about the type of interactions and the organization between PVC and EVA85 in the blends are proposed.     

Effect of supercritical carbon dioxide on polystyrene extrusion

A study on the extrusion of polystyrene was carried out using supercritical carbon dioxide (scCO₂) as foaming agent. scCO₂ modifies the rheological properties of the material in the barrel of the extruder and acts as a blowing agent during the relaxation at the passage through the die. For experiments, a single-screw extruder was modified to be able to inject scCO₂ within the extruded material. The effect of operating parameters on material porosity was studied. Samples were characterized by using water-pycnometry, mercury-porosimetry and scanning electron microscopy. Polystyrene with expansion rate about 15–25% was manufactured. A rapid cooling just downstream the die is important to solidify the structure. The die temperature allows the control of the porosity structure. CO₂ concentration shows no significant influence.     

Generation of microcellular foams of PVDF and its blends using supercritical carbon dioxide in a continuous process

Use of supercritical carbon dioxide (scCO₂) as a blowing agent to generate microcellular polymer foams (MPFs) has recently received considerable attention due to environmental concerns associated with conventional organic blowing agents. While such foams derived from amorphous thermoplastics have been previously realized, semicrystalline MPFs have not yet been produced in a continuous scCO₂ process. This work describes the foaming of highly crystalline poly(vinylidene fluoride) (PVDF) and its blends with amorphous polymers during extrusion. Foams composed of neat PVDF and immiscible blends of PVDF with polystyrene exhibit poor cell characteristics, whereas miscible blends of PVDF with poly(methyl methacrylate) (PMMA) yield foams possessing vastly improved morphologies. The results reported herein illustrate the effects of blend composition and scCO₂ solubility on PVDF/PMMA melt viscosity, which decreases markedly with increasing PMMA content and scCO₂ concentration. Morphological characterization of microcellular PVDF/PMMA foams reveals that the cell density increases as the PMMA fraction is increased and the foaming temperature is decreased. This study confirms that novel MPFs derived continuously from semicrystalline polymers in the presence of scCO₂ can be achieved through judicious polymer blending.     

Effects of supercritical carbon dioxide on crystallisation behaviour of polycarbonate/poly(methyl methacrylate) blends

SnCl₂·2H₂O-modified polycarbonate (PC)/poly(methyl methacrylate) (PMMA) (80/20?w/w) blends were prepared by melt blending using a torque rheometer. Supercritical carbon dioxide (scCO₂) has been used to induce the crystallisation of PC/PMMA blends while the crystallisation behaviour and morphology of these blend systems under different saturation temperatures, saturation pressures, saturation times and co-solvent contents were characterised by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The gravimetric experiment shows that the solubility of scCO₂ in PC/PMMA blends increases with the increase of saturation temperature, pressure and time. The DSC curves demonstrate that in these blend systems, the induced crystallisation of PC has been found and two kinds of crystals with different thicknesses exist in it. From the SEM images, it can be found that the structure of PC crystal becomes more perfect and its crystallinity also increases with the increase of saturation temperature, pressure, time and co-solvent content.     

Drying of agar gels using supercritical carbon dioxide

The use of supercritical carbon dioxide (scCO₂) for the removal of water from agar gels has been investigated and compared to air and freeze drying. Experiments were conducted to evaluate how gel formulation (with and without sucrose) and drying conditions (with and without ethanol as a co-solvent, flow rate and depressurisation rate) affected the microstructure of the gels dried using scCO₂. X-ray micro-computed tomography (X-ray micro-CT) was used to determine the voidage (% open pore space) of the dried structures, which can be used to indicate the extent of drying-induced structural collapse (in general, the lower the voidage, the greater the collapse). For formulations containing sucrose, which displayed the best structural retention, voidage was found to increase in the order: air drying (4% voidage) < supercritical drying with pure CO₂ (48%) < supercritical drying with ethanol-modified CO₂ (68%) < freeze drying (76%). The relatively high voidage of samples dried in the presence of ethanol, was due in part to foaming of the gels, hypothesised to result from an interaction between the agar and ethanol, rather than an effect of the supercritical fluid. CO₂ flow rate (1 vs. 3 l/min) during supercritical drying and depressurisation rate (0.4 vs. 1.6 MPa/min) had no effect on the dried microstructure.     

Role of supercritical carbon dioxide for selective impregnation of decrosslinking reagent into isoprene rubber vulcanizate

The behavior of supercritical CO₂ (scCO₂)/low molar mass molecule/crosslinked rubber ternary system was investigated in relation to the impregnation of reagent into the isoprene rubber (IR) vulcanizates, which was the first step of new decrosslinking reaction. The diffusion coefficient of decrosslinking reagent, diphenyl disulfide (DD), into the IR network in scCO₂ was 3.2×10⁻¹¹ m²/s. The distribution coefficient (K_c) of DD between the solvent and IR matrix was also determined for scCO₂ and toluene. The K_c for scCO₂ was higher about four orders of magnitude than that for toluene. DD was uniformly dispersed in the crosslinked IR matrix under 10 MPa at 313 K in scCO₂. These phenomena are advantages of use of scCO₂ for the effective decrosslinking reaction of IR vulcanizate.     

Polymerization of acrylonitrile in supercritical carbon dioxide

A series of fluorinated diblock copolymers, consisting of styrene (St)-acrylonitrile (AN) copolymer [poly(St-co-AN)] and poly-2-[(perfluorononenyl)oxy]ethyl methacrylate, with various compositions as well as with different molecular weights were synthesized by atom transfer radical polymerization and characterized. Dispersion polymerization of acrylonitrile in supercritical carbon dioxide (scCO₂) at 30 MPa and at 65 °C with this kind of amphiphilic block copolymer as a stabilizer and 2,2′-azobisisobutyronitrile as an initiator was investigated. The experimental results indicated that, in the presence of a small amount of poly(St-co-AN) (5 wt% to AN), spherical particles of polyacrylonitrile (PAN) were prepared with small diameter and narrow polydispersity (d_n = 153 nm, d_w/d_n = 1.12), resulting from the high stabilizing efficiency of this fluorinated block copolymer. Furthermore, the polymerization of AN in scCO₂ under different initial pressures especially under low pressure (<14 MPa) was studied. When the polymerization was carried out around the critical pressure of CO₂ (7.7-7.8 MPa), the PANs with high molecular weight (M_ν ≈ 130,000-194,000) were synthesized at high monomer conversion (>90%) no matter whether the stabilizer was added, compared to those synthesized by dispersion polymerization at 30 MPa. It was also found that the crystallinity of PAN synthesized at 7.7-7.8 MPa was somewhat higher than that synthesized at 30 MPa, while its crystallite size did not change.     

Reactive extraction of succinic acid using supercritical carbon dioxide

Reactive extraction using supercritical carbon dioxide (scCO₂) and tri-n-octylamine (TOA) was evaluated as a separation method of succinic acid from an aqueous solution. The reactive extraction of succinic acid was performed at varying initial acid concentrations in aqueous solution (0.07–0.45 mol?dm^?3), temperature (35–65°C) and pressure (8–16 MPa). The succinic acid separation was conducted in both batch mode and semi-continuous mode. The highest reactive extraction efficiency of approx. 62% was obtained for the process conducted in semi-continuous mode at 35°C and 16 MPa for the initial acid concentrations in aqueous phase of 0.39 mol?dm^?3.     

Extraction and identification of proanthocyanidins from grape seed (Vitis Vinifera) using supercritical carbon dioxide

In this study, supercritical carbon dioxide extraction of proantocyanidins (PRCs) was performed and the effect of different pressure, temperature and ethanol percentage was investigated. High performance liquid chromatography was used for the analysis of the compounds and it was found that the most effective parameter on the extraction was the amount of the ethanol percentage. Each compound was extracted from grape seeds at their maximum level when different parameters were used which was probably because of their different polarities. Gallic acid (GA), epigallocatechin (EGC) and epigallocatechingallate (EGCG) were extracted at their maximum level when the 300 bar 50 °C and 20% of ethanol was used. The maximum amount of catechin (CT) and epicatechin (ECT) were obtained when 300 bar 30 °C and 20% of ethanol was used for extraction, and 250 bar, 30 °C and 15% of ethanol was needed to extract highest amount of epicatechingallate (ECG).     

Structure and properties of highly stereoregular isotactic poly(methyl methacrylate) and syndiotactic poly(methyl methacrylate) blends treated with supercritical CO2

The structure and properties of highly stereoregular isotactic poly(methyl methacrylate) (it-PMMA) and syndiotactic poly(methyl methacrylate) (st-PMMA) blends with crystalline stereocomplex formed by supercritical CO₂ treatment at temperatures ranging from 35 to 130 °C were investigated by means of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and dynamic mechanical analysis (DMA) measurements. The melting temperature, T_m, and the heat of fusion, ΔH_m, had maximum values at about 200 °C and 25 J/g, respectively. The degree of crystallinity evaluated by WAXD ranged in value from 32 to 38%. The fringed-micellar stereocomplex crystallites were formed in case of treatment temperatures below 90 °C, and the orderliness perpendicular to the helix axis of the fringed-micellar crystallites was considered to be increased with increasing treatment temperature. In case of treatment temperature of 130 °C, the fringed-micellar crystallites and the lamellar crystallites with high orderliness parallel to the helix axis coupled with the perpendicular orderliness were formed, and the respective double endothermic peaks, T_m¹ and T_m³, were observed in DSC due to the melting of the two kinds of stereocomplex crystallites. The it-PMMA/st-PMMA blends containing the fringed-micellar crystallites maintained high values of storage modulus, E′, up to higher temperature compared with the amorphous blends. The E′ of the blend treated with CO₂ at 130 °C decreased twice at temperatures corresponding to T_m¹ and T_m³.     

Acetylation of plant cellulose fiber in supercritical carbon dioxide

Natural cellulosic ramie fiber was acetylated using supercritical carbon dioxide (sc-CO₂) as a reaction medium. The structure and properties of the acetylated fibers were investigated using infrared spectroscopy, scanning electron microscopy, X-ray diffraction (including synchrotron microbeam X-ray diffraction), nano-Raman scattering, and a tensile test. The acetylation reaction proceeded without using an organic solvent, and it reached to the core part of the fiber within a short period while maintaining the fiber morphology. The crystallites of cellulose triacetate II and cellulose coexist in the fiber. The acetylated fiber with an average degree of substitution of 1.9 showed high modulus (34.5 GPa) and high strength (763 MPa), which are the highest values for cellulose diacetate so far reported to date.     

Iodine doping of poly(3‐undecylbithiophene) and its composites with polystyrene using supercritical carbon dioxide

Partially doped conductive poly(3‐undecylbithiophene) and its composites with porous, crosslinked polystyrene were chemically doped with iodine using supercritical carbon dioxide to transport iodine to the conductive regions of the composite. The amount of iodine incorporated into the composite increased from 9.3 wt % at ambient conditions without carbon dioxide to 21.4 wt % in the presence of supercritical carbon dioxide. The conductivity of the composite increased by up to two orders of magnitude with iodine doping using supercritical carbon dioxide. The highest conductivity was obtained in samples treated at moderate temperatures and pressures (313 K and 20.7 MPa). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3876–3881, 2003     

Solubility of non-ionic poly(fluorooxetane)-block-(ethylene oxide)-block-(fluorooxetane) surfactants in carbon dioxide

The impact of side chain and midblock length on the solubility of ABA triblock copolymers of fluorooxetane-(ethylene oxide)-fluorooxetane in carbon dioxide is examined. The use of short fluorinated side chains instead of long fluorinated chains prevents issues with bioaccumulation of the degradation products of the surfactant. At 40 °C for the same degree of polymerization, increasing the number of perfluoro-units from one to four results in a non-monotonic change in the cloud point pressure; the cloud point pressure decreases as the side chain is increased from perfluoromethyl to perfluoroethyl. However, further increasing the fluorinated side chain to perfluorobutyl results in a significant increase in the cloud point. However when the temperature is increased to 60 °C, the cloud point pressure for the surfactants with perfluoroethyl and perfluorobutyl side chains is statistically similar, while the perfluoromethyloxetane based surfactant requires a substantially larger pressure to obtain comparable solubility. An increase in cloud point pressure is observed when increasing the hydrophilic ethylene oxide segment. These results illustrate that commercially available fluorooxetane-(ethylene oxide)-fluorooxetane surfactants are highly soluble in CO₂.     

利用超临界二氧化碳流体脱硫再生丁基橡胶

研究了硫黄硫化的丁基橡胶在超临界二氧化碳流体辅助下的脱硫降解行为,讨论了脱硫工艺的条件,并通过凝胶渗透色谱、核磁共振、差示扫描量热等对丁基再生胶的结构和性能进行了考察。结果表明,在二氧化碳的超临界状态下丁基橡胶的脱硫降解更加充分。脱硫的最佳工艺条件为: 反应温度180 ℃,反应压力14. 1 MPa,脱硫剂二苯基二硫的用量为橡胶质量的8%; 经过120 min 脱硫反应后丁基再生胶中溶胶的质量分数为98. 5%。在有热降解和脱硫剂参与的脱硫反应的共同影响下,丁基再生胶中溶胶的数均分子量降至原胶的40%左右; 再生胶主链上接枝了部分脱硫剂的苯环; 硫化和脱硫过程中在接枝于主链上的极性基团的影响下,再生胶中溶胶主链双键氢的振动峰几乎消失,但再生胶的玻璃化转变温度并没有明显变化。     

超临界CO2萃取丁香挥发油的实验研究

采用正交实验法对超临界CO2萃取丁香挥发油的条件进行了研究。考察了萃取温度、压力、CO2流量等因素在不同水平下对丁香挥发油提取率的影响。得到了超临界C02萃取丁香挥发油的最佳实验条件：萃取压力30MPa、温度40℃、CO2流量40kg／h和萃取时间80min,得率为20．62％。与水蒸气蒸馏法比较,超临界CO2萃取的收率高,萃取时间短。     

Dispersion polymerization of 2-hydroxyethyl methacrylate stabilized by a hydrophilic/CO2-philic poly(ethylene oxide)-b-poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) (PEO-b-PFDA) diblock copolymer in supercritical carbon dioxide

Dispersion polymerization of 2-hydroxyethyl methacrylate (HEMA) has been successfully performed in supercritical carbon dioxide at P=370 bar and T=65 °C with azobis(isobutyronitrile) as initiator and a hydrophilic/CO₂-philic poly(ethylene oxide)-b-poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) (PEO-b-PFDA) block copolymer as steric stabilizer. The PEO-b-PFDA (2K/21K) block copolymer was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Spherical particles of poly(HEMA) were obtained in the range of 200-400 nm diameter size with a narrow particle size distribution (D_w/D_n<1.1). The effect of the stabilizer concentration on the dispersion polymerization was investigated from 20 w/w% down to 3.5 w/w% versus HEMA. Precipitation polymerization in the absence of stabilizer lead to the formation of large aggregates of partially coalesced particles whereas discrete spherical particles of poly(HEMA) were obtained by dispersion polymerization even at low concentration of PEO-b-PFDA (3.5 w/w% versus HEMA).     

Solubility of chlorpheniramine maleate in supercritical carbon dioxide

Solubility of chlorpheniramine maleate in supercritical carbon dioxide at different temperatures (308–338 K) and pressures (160–400 bar) is measured using static method coupled with gravimetric method. The measured solubility data demonstrated that the solubility of chlorpheniramine maleate was changed between 1.54 × 10⁻⁵ and 4.26 × 10⁻⁴ based on the mole fraction as the temperature and pressure are changed. The general trend of measured solubility data shows a direct effect of pressure and temperature on the solubility of chlorpheniramine maleate. Finally, the obtained solubilities correlated using four semi-empirical density-based correlations including Mendez Santiago–Teja (MST), Kumar and Johnston (KJ), Bartle et al., and Chrastil models. Although the results of modeling showed that the KJ model leads to the average absolute relative deviation percent (AARD %) of 8.1% which is the lowest AARD %, deviation of other utilized correlations are rather the same.     

Synthesis of cross-linked poly(4-vinylpyridine) and its copolymer microgels using supercritical carbon dioxide: Application in the adsorption of copper(II)

Compared with conventional precipitation polymerization method, cross-linked poly(4-vinylpyridine) (P4VP) and its microgels copolymerized with α-methacrylic acid (MAA) were synthesized through a new route of stabilizer-free polymerization in supercritical fluids. The yellow, dry, fine powders were directly obtained from precipitation polymerization of 4-vinylpyridine in supercritical carbon dioxide (scCO₂) at pressures ranging from 70.0 to 230 bar, using N,N′-methylenebisacrylamide as cross-linker. The effects of the reaction pressure, cross-linker ratio, initiator concentration, and reaction time were investigated. The capacity of this microgel for adsorption of copper(II) was also studied. At higher cross-linker concentrations, a high yield of the cross-linked P4VP microgel was generated in scCO₂, and its particle size was less than 300 nm. Polymerization of cross-linked P4VP in scCO₂ was extremely sensitive to the density of the continuous phase. The adsorption followed the Langmuir isotherm. The adsorption capacities of cross-linked P(4VP-co-MAA) and cross-linked P4VP were 47.2 and 26.9 mg g⁻¹, respectively.