Regeneration of nanoporous crystalline syndiotactic polystyrene by supercritical CO2

Guest desorption procedures for s‐PS clathrate samples, leading to formation and regeneration of the nanoporous δ phase, are compared. An extraction procedure, based on supercritical carbon dioxide, allows an easy and fast recovery of the guest molecules operating under relatively mild conditions (90–200 bar, 40°C) and generates a completely empty δ form, also starting from the most stable s‐PS clathrate forms. In agreement with a previously proposed crystal structure of the nanoporous δ form, X‐ray diffraction patterns of δ form powders obtained by this procedure do not show the peak, which is reduced but still apparent in samples extracted with previous procedures based on boiling solvents. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2077–2082, 1999     

Mesoporous silica particles grafted with polystyrene brushes as a nucleation agent for polystyrene supercritical carbon dioxide foaming

In this study, spherical ordered mesoporous silica (s‐OMS) was applied as a new type of nucleating agent in polystyrene (PS) foaming with supercritical CO₂ as a blowing agent. These s‐OMS particles were modified by the selective grafting of PS brushes on the outside surface, by which the mesoporous structure inside particles could be maintained. Transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, and Brunauer–Emmett–Teller surface area analysis were used to characterize the structure of the original and modified particles; these indicated that the PS brushes were grafted on the outside surface and the inside porous structure were maintained. PS/s‐OMS–PS composites were prepared by a solution blending method, and the s‐OMS–PS particles could have been well dispersed in the PS matrix because of the surface modification. Subsequently, PS and composite microcellular foams were prepared by a batch foaming process, and the morphology characterization on these foams showed that the s‐OMS particles exhibited an excellent heterogeneous effect on PS foaming. The heterogeneous effect became more significant when the foaming temperature or saturation pressure was low. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4308–4317, 2013     

Preparation of Nanowells on a PS‐b‐PMMA Copolymer Thin Film by CO2 Treatment

Ordered nanowells with diameters of ca. 40 nm and depth of 1–2 nm were prepared on a poly(methyl methacrylate) (PMMA) spherical domain, which was exposed on the polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) copolymer thin film. The PS‐b‐PMMA film formed spherical PMMA domains after the film was annealed above the order–disorder transition temperature. CO₂ was dissolved into the PS‐b‐PMMA thin film at 8.6 MPa and at a temperature of 20 °C. The release of CO₂‐pressure at the same temperature created the nanowell on the PMMA domain. The temperature and pressure to create nanowells in the PMMA domain affected the possibility of nanowell's formation.

     

Toughness enhancement of high‐impact polystyrene based on γ‐radiation vulcanized natural rubber latex by using block copolymer

Polyisoprene‐block‐polystyrene‐block‐polyisoprene (ISI) was synthesized by the iniferter route and its use, as compared to a commercial polystyrene‐block‐polyisoprene‐block‐polystyrene (SIS), in the enhancement of the toughness of high‐impact polystyrene (HIPS), prepared by the γ‐radiation vulcanized natural rubber (RVNR) latex/phase transfer/bulk polymerization technique, was investigated. Addition of 5% SIS was adequate as an interfacial agent, which effectively increased the unnotched Izod impact energy of HIPS, whereas use of 10% of ISI was required. A long polyisoprene block with two polystyrene segments of SIS was favorable for compatibilization of HIPS. Transmission electron micrographs revealed the uniform distribution of the block copolymer at the shell region of the rubber particle. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1307–1316, 2002     

Foam Processing and Cellular Structure of Polycarbonate‐Based Nanocomposites

Summary: Via a batch process in an autoclave, foam processing of intercalated PC/clay nanocomposites, having different amounts of clay, has been conducted using supercritical CO₂ as a foaming agent. The cellular structures obtained from various foaming temperature‐CO₂ pressure ranges were investigated by SEM. The incorporation with nanoclay‐induced heterogeneous nucleation occurs because of a lower activation energy barrier compared with homogeneous nucleation as revealed by the characterization of the interfacial tension between bubble and matrix. The controlled structure of the PCCN foams changed from microcellular (d ? 20 µm and N_c ? 1.0 × 10⁹ cells · cm^?3) to nanocellular (d ? 600 nm and N_c ? 3.0 × 10¹³ cells · cm^?3). The mechanical properties of PCCN foams under compression test were discussed.

TEM micrograph for the structure of the cell wall foamed at 160 °C.     

Controlling the structure of a porous polymer by coupling supercritical CO2 and single screw extrusion process

A study on the extrusion of Eudragit E100 was carried out using supercritical carbon dioxide (scCO₂) as plasticizer and 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 when flowing through the die. For experiments, a single‐screw extruder was modified to be able to inject scCO₂ within the extruded material. The aim is to determine a correlation between operating conditions and foam structure. The effect of three parameters was studied: the temperature in the die and in the metering zone, the screw speed, and the volumetric flow rate of CO₂. An increase in temperature enhances the expansion rate and the average pore diameter and appears to be the most significant parameter. The effect of CO₂ concentration is significant at small concentrations only: the higher the CO₂ concentration, the lower the pore density and the higher both the pore diameter and the expansion rate. The effect of the screw speed is tricky because a variation of this speed involves a decrease of CO₂ weight ratio. This study shows that the structure of the extrudates does not evolve with a coupling of screw speed increase and a subsequent CO₂ weight ratio decrease. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

CO2‐assisted polymer processing: A new alternative for intractable polymers

CO₂‐assisted polymer processing is proposed as an alternative route for intractable and high molecular weight polymers based on the plasticization effects of CO₂ and its direct effect on the melting behavior of semicrystalline polymers. A modified processing system was used to process a variety of polymers in the presence of high‐pressure CO₂. The system includes an extruder that was modified to allow for high pressures created by the injection of CO₂. The new design includes a modified feed section that allows a given mass of polymer to interact with CO₂ before and during the extrusion process. The inherent shear mixing and the presence of CO₂ allow for a specific control over the extrudate morphology. Results suggest that this alternative design provides a new and easy route to melt process high melt viscosity polymers of commercial importance, such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), and syndiotactic polystyrene (s‐PS). The increased processability of these systems in CO₂ is related to the plasticization effect of CO₂ that was quantified through a depression in the glass‐transition temperature according to the Chow model. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1501–1511, 2004     

Atom transfer radical polymerization grafting of highly functionalized polystyrene and poly(4‐methylstyrene) macroinitiators with tert‐butyl acrylate

Two monodisperse graft copolymers, poly(4‐methylstyrene)‐graft‐poly(tert‐butyl acrylate) [number‐average molecular weight (M_n) = 37,500, weight‐average molecular weight/number‐average molecular weight (M_w/M_n) = 1.12] and polystyrene‐graft‐poly(tert‐butyl acrylate) (M_n = 72,800, M_w/M_n = 1.12), were prepared by the atom transfer radical polymerization of tert‐butyl acrylate catalyzed with Cu(I) halides. As macroinitiators, poly{(4‐methylstyrene)‐co‐[(4‐bromomethyl)styrene]} and poly{styrene‐co‐[4‐(1‐(2‐bromopropionyloxy)ethyl)styrene]}, carrying 40% of the bromoalkyl functionalities along the chain, were used. The dependencies of molecular parameters on monomer conversion fulfilled the criteria for controlled polymerizations. In contrast, the dependencies of monomer conversion versus time were nonideal; possible causes were examined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2930–2936, 2002     

The synergy of supercritical CO2 and supercritical N2 in foaming of polystyrene for cell nucleation

This study examines the foaming behaviour of polystyrene (PS) blown with supercritical CO₂–N₂ blends. This is achieved by observing their foaming processes in situ using a visualization system within a high-temperature/high-pressure view-cell. Through analyzing the cell nucleation and growth processes, the foaming mechanisms of PS blown with supercritical CO₂–N₂ blends have been studied. It was observed that the 75% CO₂–25% N₂ blend yielded the highest cell densities over a wide processing temperature window, which indicates the high nucleating power of supercritical N₂ and the high foam expanding ability of supercritical CO₂ would produce synergistic effects with that ratio in batch foaming. Also, the presence of supercritical CO₂ increased the solubility of supercritical N₂ in PS, so the concentration of dissolved supercritical N₂ was higher than the prediction by the simple mixing rule. The additional supercritical N₂ further increased the cell nucleation performance. These results provide valuable directions to identify the optimal supercritical CO₂–N₂ composition for the foaming of PS to replace the hazardous blowing agents which are commonly used despite their high flammability or ozone depleting characteristics.     

Preparation of polystyrene/montmorillonite nanocomposites in supercritical carbon dioxide

The preparation of polystyrene (PS)/montmorillonite (MMT) composites in supercritical carbon dioxide (SC? CO₂) was studied. Lipophilic organically modified MMT can be produced through an ion‐exchange reaction between native hydrophilic MMT and an intercalating agent (alkyl ammonium). PS/clay composites were prepared by free‐radical precipitation polymerization of styrene containing dispersed clay. X‐ray diffraction and transmission electron microscopy indicated that intercalation of MMT was achieved. PS/clay composites have a higher thermal decomposition temperature and lower glass‐transition temperature than pure PS. The IR spectrum analysis showed that the solvent of SC? CO₂ did not change the structures of the PS molecules, but there were some chemical interactions between the PS and the clay in the composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 22–28, 2005     

Influence of supercritical CO2 on the interactions between maleated polypropylene and alkyl‐ammonium organoclay

Supercritical carbon dioxide (scCO₂) has been proposed as an effective exfoliating agent for the preparation of polymer‐layered silicate nanocomposites, though there is limited fundamental understanding of this mechanism. This study looks at the interactions of this unique green solvent with three maleated polypropylenes of varying anhydride content and molecular size with an alkyl‐ammonium organoclay. Mixtures of compatibilizers and organoclay were melt‐annealed in a high pressure batch vessel at 200°C and subjected to either a blanket of nitrogen or scCO₂ at a pressure of 9.7 MPa. The structures and properties of these melt‐annealed mixtures were characterized by X‐ray diffraction, transmission electron microscopy, Fourier Transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and contact angle measurement. The results indicate that the plasticizing influence of scCO₂ aided intercalation and exfoliation for intercalants of moderate molecular size and anhydride content which would otherwise have limited diffusion into the clay galleries. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane via polysiloxane‐based macroinitiator in supercritical CO2

Polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane (PDMS‐b‐PS‐b‐PDMS) was synthesized by the radical polymerization of styrene using a polydimethylsiloxane‐based macroazoinitiator (PDMS MAI) in supercritical CO₂. PDMS MAI was synthesized by reacting hydroxy‐terminated PDMS and 4,4′‐azobis(4‐cyanopentanoyl chloride) (ACPC) having a thermodegradable azo‐linkage at room temperature. The polymerization of styrene initiated by PDMS MAI was investigated in a batch system using supercritical CO₂ as the reaction medium. PDMS MAI was found to behave as a polyazoinitiator for radical block copolymerization of styrene, but not as a surfactant. The response surface methodology was used to design the experiments. The parameters used were pressure, temperature, PDMS MAI concentration and reaction time. These parameters were investigated at three levels (?1, 0 and 1). The dependent variable was taken as the polymerization yield of styrene. PDMS MAI and PDMS‐b‐PS‐b‐PDMS copolymers obtained were characterized by proton nuclear magnetic resonance and infrared spectroscopy. The number‐ and weight‐average molecular weights of block copolymers were determined by gel permeation chromatography. Copyright © 2004 Society of Chemical Industry     

Comparative study on foaming process of thermoplastic polyester and polyether polyurethane with supercritical CO2 as foaming agent

ABSTRACT

The aim of this study was the comparison of beads foaming process and synergistic effect of foaming process parameters on melting crystalline characteristics between thermoplastic polyester and polyether polyurethane(TPU) via batch process using supercritical CO₂(scCO₂) as blowing agent. Method was based on the generation of expandable TPU foam beads (ETPU) prepared by self-designed autoclave foaming apparatus. The surface morphology, cell structure, and crystalline melting characteristics of the ETPU depending on the processing parameters, such as saturation pressure (P_f), saturation temperature (T_f), and saturation time (t_f), were investigated. Results demonstrated both ETPU exhibited fine closed cell morphology with polygons structure and would induce the disappearance of multiple endothermic peaks during the foam process. As any of those three process parameters increased, the HS content, high crystalline melting and E_r were improved, while with regard to cell structure, P_f demonstrated the opposite effect compared with T_f and t_f. Comparing with polyether TPU, polyester TPU possess a larger cell density and a clear bimodal cell structure could be found under certain condition, while beads foaming process had a greater impact on polyether TPU, which had a low density and the appropriate t_f is 2h.     

Towards a one‐pot synthesis of a polystyrene–PMMA block copolymer via atom‐transfer radical polymerization

The solution atom‐transfer radical copolymerization of styrene and methyl methacrylate in butyl acetate at 110 °C in the presence of Cu(II) bromide and 2,2′‐bipyride was investigated. Polystyrene was polymerized by atom‐transfer radical polymerization using benzyl bromide as initiator and MMA was then added to the system. Block copolymers were formed when MMA was added at ≤90% styrene conversion. Molecular weight distributions (M_w/M_n) of the block copolymers were ≤1.5. The possibility of end‐capping the polystyrene precursor as a means of improving its initiating efficiency towards MMA was also investigated but did not improve the system. © 2002 Society of Chemical Industry     

Enhancement of the high‐temperature utility of a polystyrene‐b‐poly(ethylene‐co‐butylene)‐b‐polystyrene block copolymer by friedel–crafts naphthoylation

A procedure was developed for the Friedel–Crafts naphthoylation of the polystyrene segments of a polystyrene‐b‐poly(ethylene‐co‐butene)‐b‐polystyrene (SEBS) triblock copolymer. It was possible to obtain up to 72% 1‐naphthoylation or 100% 2‐naphthoylation of the polystyrene segments in the copolymer. Naphthoylation could also be accomplished using trifluoromethanesulfonic acid as a catalyst. The naphthoylated products were characterized by ¹H‐NMR spectroscopy, size‐exclusion chromatography, and dynamic mechanical thermal analysis. The mechanical properties of the original and naphthoylated polymers were measured from 25 to 125°C. The results obtained indicate that naphthoylation enhances the tensile properties of the polymers at elevated temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1289–1295, 2003     

Compatibilization of high‐impact polystyrene/high‐density polyethylene blends by styrene/ethylene–butylene/styrene block copolymer

Compatibilization of polymer blends of high‐impact polystyrene (HIPS) and high‐density polyethylene (HDPE) blend by styrene/ethylene–butylene/styrene (SEBS) was elucidated. Polymer blends containing many ratios of HIPS and HDPE with various concentrations of SEBS were prepared. The Izod impact strength and elongation at break of the blends increased with increases in SEBS content. They increased markedly when the HDPE content was higher than 50 wt %. Tensile strength of blends increased when the SEBS concentration was not higher than 5 pphr. Whenever the SEBS loading was higher than 5 pphr, the tensile strength decreased and a greater decrease was found in blends in which the HDPE concentration was more than 50 wt %. The log additivity rule model was applied to these blends, which showed that the blends containing the HIPS‐rich phase gave higher compatibility at the higher shear rates. Surprisingly, the blends containing the HDPE‐rich phase yielded greater compatibility at the lower shear rates. Morphology observations of the blends indicated better compatibility of the blends with increasing SEBS concentration. The relaxation time (T₂) values from the pulsed NMR measurements revealed that both polymer blends became more compatible when the SEBS concentration was increased. When integrating all the investigations of compatibility compared with the mechanical properties, it is possible to conclude that SEBS promotes a certain level of compatibilization for several ratios of HIPS/HDPE blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 742–755, 2004     

Synthesis and characterization of poly(n‐butyl methacrylate)‐b‐polystyrene diblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate) (PBMA)‐b‐polystyrene (PSt) diblock copolymers were synthesized by emulsion atom transfer radical polymerization (ATRP). PBMA macroinitiators that contained alkyl bromide end groups were obtained by the emulsion ATRP of n‐butyl methacrylate with BrCH₃CHCOOC₂H₅ as the initiator; these were used to initiate the ATRP of styrene (St). The latter procedure was carried out at 85°C with CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine as the catalyst and polyoxyethylene(23) lauryl ether as the surfactant. With this technique, PBMA‐b‐PSt diblock copolymers were synthesized. The polymerization was nearly controlled; the ATRP of St from the macroinitiators showed linear increases in number‐average molecular weight with conversion. The block copolymers were characterized with IR spectroscopy, ¹H‐NMR, and differential scanning calorimetry. The effects of the molecular weight of the macroinitiators, macroinitiator concentration, catalyst concentration, surfactant concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are also reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2123–2129, 2005     

Synthesis and characterization of novel polystyrene‐block‐polyurethane‐block‐polystyrene tri‐block copolymers through atom transfer radical polymerization

Background: Radical polymerization is used widely to polymerize more than 70% of vinyl monomers in industry, but the control over molecular weight and end group of the resulting polymers is always a challenging task with this method. To prepare polymers with desired molecular weight and end groups, many controlled radical polymerization (CRP) ideas have been proposed over the last decade. Atom transfer radical polymerization (ATRP) is one of the successful CRP techniques. Using ATRP, there is no report on the synthesis of polystyrene‐block‐polyurethane‐block‐polystyrene (PSt‐b‐PU‐b‐PSt) tri‐block copolymers. Hence this paper describes the method of synthesizing these tri‐block copolymers. To accomplish this, first telechelic bromo‐terminated polyurethane was synthesized and used further to synthesize PSt‐b‐PU‐b‐PSt tri‐block copolymers using CuBr as a catalyst and N,N,N,N″,N″‐pentamethyldiethylenetriamine as a complexing agent. Results: The ‘living’ nature of the initiating system was confirmed by linear increase of number‐average molecular weight and conversion with time. A semi‐logarithmic kinetics plot shows that the concentration of propagating radical is steady. The results from nuclear magnetic resonance spectroscopy, gel permeation chromatography and differential scanning calorimetry show that the novel PSt‐b‐PU‐b‐PSt tri‐block copolymers were formed through the ATRP mechanism. Conclusion: For the first time, PSt‐b‐PU‐b‐PSt tri‐block copolymers were synthesized through ATRP. The advantage of this method is that the controlled incorporation of polystyrene block in polyurethane can be achieved by simply changing the polymerization time. Copyright © 2007 Society of Chemical Industry     

Synthesis of block copolymers with thermodynamically compatible chain segments: di‐ and triblock copolymers of polystyrene and poly(2,6‐dimethyl‐1,4‐phenylene oxide)

Mono‐ and bifunctional poly(phenylene oxide) (PPO) macroinitiators for atom transfer radical polymerization (ATRP) were prepared by esterification of mono‐ and bishydroxy telechelic PPO with 2‐bromoisobutyryl bromide. The macroinitiators were used for ATRP of styrene to give block copolymers with PPO and polystyrene (PS) segments, namely PPO‐block‐PS and PS‐block‐PPO‐block‐PS. Various ligands were studied in combination with CuBr as ATRP catalysts. Kinetic investigations revealed controlled polymerization processes for certain ligands and temperature ranges. Thermal analysis of the block copolymers by means of DSC revealed only one glass transition temperature as a result of the compatibility of the PS and PPO chain segments and the formation of a single phase; this glass transition temperature can be adjusted over a wide temperature range (ca 100–199 °C), depending on the composition of the block copolymer. Copyright © 2005 Society of Chemical Industry     

Deformation and alignment of lamellae in melt extension of blends of a styrene‐butadiene block copolymer with polystyrene

The development of the morphology and the alignment of lamellae in melt elongation of blends of an asymmetric linear styrene‐butadiene block copolymer (LN3) and polystyrene (PS 158K) was investigated. PS 158K and LN3 formed two‐phase polymer blends with PS 158K resp. LN3 inclusions, depending on the concentration of polystyrene. The block copolymer was arranged in a lamellar phase with a lamellae thickness of ～ 13 nm. Our rheological experiments revealed that the complex modulus, the elongational viscosity and the recovered stretch of the blends primarily resulted from a superposition of the properties of the blend components. In melt elongation, pure LN3 started to crumple at a small Hencky strain. In the blends, the presence of the PS 158K inclusions led to a macroscopically more uniform elongation, but with an anisotropic Poisson ratio. The LN3 inclusions in the PS 158K matrix were deformed into a filament‐like shape. In the blends with a LN3 matrix the alignment of the block copolymer lamellae parallel to the loading direction increased with applied extensional strain. In the latter case, the lamellae thickness did not decrease significantly. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009