Mass transfer and depolymerization of styrene in polystyrene

This work shows how laboratory experiments may provide parameters which are useful in modeling a commercial process of polystyrene devolatilization. Such processes often occur at temperatures where depolymerization of polystyrene to monomer may be significant. Polystyrene devolatilizers function by forming thin films of the polymer, with styrene loss by flashing and diffusion and styrene generation by depolymerization. The modeling parameters of importance are: depolymerization rate constant, monomer diffusivity, and thermodynamic equilibrium polymer-vapor partition coefficient. Typical levels of styrene in polystyrene in the last stage of devolatilization are 100 to 1000 ppm. Pressures and temperatures in the devolatilizer are often less than 10 torr and greater than 200°C. For styrene-polystyrene the desired parameters have not been reported, nor apparently measured, at the concentration, pressure and temperature levels of interest.     

Continuous production of solid polystyrene in back‐mixed and linear‐flow reactors

A mathematical model has been developed to predict the steady state performance of a continuous bulk styrene polymerization process with catalytic initiation for solid polystyrene. The polymerization section contains one boiling CSTR, followed by multiple linear‐flow reactors. The devolatilization section consists of two polymer pre‐heaters and two high‐solids flashes. The polymer moment equations were solved simultaneously with the reactor modeling equations. The non‐linear algebraic equations were solved by a Newton‐Raphson iteration technique to give the steady‐state styrene monomer weight fraction in a CSTR. The coupled, non‐linear ordinary differential equations were numerically integrated using a single‐step, 4th‐order Runge‐Kutta technique, followed by a multi‐step Adams‐Moulton technique. The resulting computer simulation model is capable of evaluating how the production rate and product quality are affected by feed composition, temperature, initiator type, initiator concentration, and residence time. Several case studies were given for commercially important crystal‐clear and impact‐resistant resins. A binary initiation system gives a good balance of monomer conversion, polymer molecular weights, and rubber grafting compared to a single initiation system. The styrene dimer/trimer occur in low concentrations but can be substantially reduced with a low temperature initiator. The ideal mean residence time is approximately one minute or less in a shell‐and‐tube devolatilization pre‐heater. Low flash chamber vacuum is more effective than high polystyrene melt temperature to reduce the volatile content of the final product. The water injected to the low volatile melt shows promising improvement in the second‐stage polystyrene devolatilization.     

High‐pressure phase equilibria for a styrene/CO2/polystyrene ternary system

To reveal the possibility of supercritical (SC)‐CO₂‐assisted devolatilization of polystyrene, the equilibrium composition data for the CO₂ phase in a styrene/CO₂/polystyrene ternary system is determined by a semistatic experimental technique. The parameters in the lattice–fluid equation of state of Sanchez and Lacombe are determined for the investigated system. The distribution coefficients of styrene between the polymer and the supercritical fluid phases are investigated experimentally at 318 and 328 K over the pressure range of 12–20 MPa. The binary interaction parameter between styrene and CO₂ is obtained by regression of the vapor–liquid equilibrium data. The interaction parameter between CO₂ and polystyrene is calculated by using the sorption data from the literature, and the interaction parameter between styrene and polystyrene is optimized by using the measured data of this study. The investigation of the distribution coefficients indicates that styrene can be removed from polystyrene by SC‐CO₂ at near room temperature and moderately high pressures. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1938–1944, 2002     

Thermal and chemical recycle of waste polymers

Catalytic degradations of polyethylene into fuel oils and of polystyrene into styrene monomer have been studied using solid acids and bases as catalysts. Solid acids such as silica-aluminas and ZSM-5 zeolite were found to be effective to degrade waste polyethylene into fuel oils, and solid bases such as BaO and K₂O were concluded to be effective to convert waste polystyrene into styrene monomer. A design of recyclable polystyrene films will be briefly mentioned.     

Polymerization as a means of stabilization for polystyrene

General purpose polystyrene prepared by conventional radical techniques contains a head‐to‐head unit as a consequence of polymerization termination by radical coupling. As has been previously demonstrated, thermal stress promotes homolysis of the bond linking the head‐to‐head components. The macroradicals that were generated depolymerize rapidly to generate styrene monomer. This decomposition during processing can lead to finished articles containing objectionable levels of styrene monomer, particularly for food packaging applications in which even low levels of monomer can promote objectionable taste and aroma. Polymer containing no head‐to‐head units should not be prone to this facile decomposition. In this instance, polystyrene has been prepared by nitroxyl‐mediated polymerization of styrene monomer followed by reductive removal of nitroxyl end groups. Polymer prepared in this manner contains no head‐to‐head units and displays thermal stability much greater than that observed for conventional polystyrene. A direct comparison of the stability for the two polymers is readily available by thermogravimetric techniques. A quantitative reflection of the difference in stability is available from the rate constants for the respective decompositions. decompositions. J. VINYL ADDIT. TECHNOL., 12:198–203, 2006. © 2006 Society of Plastics Engineers     

The influence of residual styrene monomer,benzaldehyde, and microbial activity on the surface properties of polystyrene latices

The influence of residual styrene monomer and benzaldehyde on the surface properties of polystyrene latices has been considered. These materials are commonly found after emulsion polymerisation and their complete removal by dialysis is almost impossible. Steam stripping at reduced pressure (nitrogen atmosphere, < 350K) can be used to remove the last traces of styrene and benzaldehyde from polystyrene, but this process results in some degree of hydrolysis of the surface sulphate groups. Latices are easily contaminated by microorganisms, especially those which are airborne. This can occur during cleaning and/or storage. Microorganisms can survive and multiply in suitable latex environments and can result in the destabilisation and subsequent flocculation of the latex. Controlled experiments with a latex dosed with various levels of a penicillium type fungus demonstrated the possibility that enzymes (classified as aryl sulphate sulphohydrolases - E. C. 3.1.6.1.) were produced which resulted in the rapid hydrolysis of surface sulphate groups. Fungal growth was accompanied by the release of weak acids and metabolites which were titrated in the aqueous phase. Careful consideration should be given to the conditions of latex preparation, cleaning and storage, e.g. use of autoclaved water and γ-irradiation techniques, which will reduce the possibility of microbial contamination. Routine tests for bacteria and fungi should be carried out by plating on microbiological media, since the usual tests for protein such as the Folin-Ciocalteu are insensitive at the low levels of contamination which may be present.     

Approaches to branched polystyrene using bulk free-radical polymerization

Preparation of branched polystyrene using continuous bulk styrene polymerization is extremely difficult due to gel formation and can even lead to reactor plugging. This investigation explores the concept of post-polymerizer branching by placing latent functional groups along the polymer backbone which couple during high-temperature devolatilization of the polymerized effluent. The latent functional monomer pair investigated is glycidyl methacrylate and acrylic acid. The key to producing a branched polystyrene that is thermally stable is to add one of the latent functional monomers in large excess, making the other monomer the limiting reagent. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 683–687, 1997     

注水脱挥系统在聚苯乙烯生产中的应用

在聚苯乙烯生产装置投用注水系统进行脱挥,分析了聚苯乙烯残留单体含量的主要影响因素;对注水系统提出了改进建议。     

聚合物系动态超临界流体脱挥

A number of studies have been reported on the applications of supercritical fluids to polymeric processes. The presence of volatiles can affect the end-use properties of polymer materials. Therefore, these volatiles must be reduced to a level below the maximum permissible limit. Conventional heat-relevant techniques for polymer devolatilization sometimes have limited effectiveness. Devolatilization with supercritical fluids, however, can enhance removal of volatiles from polymers. A model for diffusion-limited extraction is used to characterize dynamic supercritical fluid devolatilization of spherical polymer particles. The rate of supercritical fluid devolailization for styrene/polystyrene system is measured at 343 K and 18 MPa and at CO2 flow rate of 1.93, 3.27 and 5.62 L·min^-1, respectively. The model analysis, which is consistent with experimental results, indicates that the supercritical fluid devolatilization is not solubility-limited but diffusion-limited when CO2 flow rate is above 4.00 L·min^-1.     

苯乙烯/二氧化碳/聚苯乙烯三元混合物的相平衡预测

A lattice fluid model,Sanchez-Lacombe equation,is used to predict the phase behavior for a styrene/CO2/polystyrene ternary system.The binary parameters involved in the equation were optimized using experimental data.Phase diagrams and the distribution coefficients of styrene between polymer phase and fluid phase are obtained over a wide rang of pressure,temperature and composition.The analysis of ternary phase diagrams indicates that this system at relatively high pressure or low temperature may display two-phase equilibrium,and at low pressures or high temperatures three-phase equilibrium may appear.The distribution coefficients of styrene between the fluid phase and the polymer phase increase asymptotically to unity when the concentration of styrene increases.The results provide thermodynamic knowledge for further exploitation of supercritical carbon dioxide assisted devolatilization and impregnation.     

Castor-oil-based interpenetrating polymer networks: Synthesis and characterization

Castor oil was polymerized and crosslinked with sulfur or diisocyanates to form the vulcanized and urethane derivatives, respectively. Both types were swollen with a plastic-forming monomer plus crosslinker, and a second polymerization was carried out in situ. Polyblends were also made by emulsion polymerization of styrene and methyl methacrylate employing hydrolyzed castor oil as the soap. In all three polymerizations, a wide range of compositions was obtained. The resulting interpenetrating polymer networks were characterized using electron microscopy, modulus–temperature measurements, and stress–strain analysis. The polystyrene phase size of the castor oil–urethane/polystyrene IPN was shown to decrease with increased crosslinking of the castor oil component and with increased polystyrene contents. The modulus–temperature study showed two distinct glass transitions in all cases, with evidence of significant mixing of the two components in many cases. The stress–strain results show that some of the IPN's behave as reinforced, highly extensible elastomers at low polystyrene levels, and a rubber-toughened plastics at high levels of polystyrene or crosslinking.     

In situ sol‐gel process of polystyrene/silica hybrid materials: Effect of silane‐coupling agents

The polystyrene–silica hybrid materials have been successfully prepared from styrene and tetraethoxysilane in the presence of silane‐coupling agents by an in situ sol‐gel process. Triethoxysilyl group can be incorporated into polystyrene as side chains by the free‐radical copolymerization of polystyrene with silane‐coupling agents, and simultaneously polystyrene–silica hybrid materials with covalent bonds between two phases were formed via the sol‐gel reaction. The 3‐(trimethoxysilyl)‐propyl‐methacrylate (MPS) systems were found to be more homogeneous than the corresponding allytrimethoxysilane hybrid system of equal molar content. In the MPS‐introduced system, the thermal properties of the materials were greatly affected by the presence of MPS. FTIR results indicate successful formation of the silica networks and covalent bonding formation of coupling agents with styrene. The homogeneity of polystyrene–silica systems was examined by scanning electron microscope and atomic force microscope. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2074–2083, 2002     

Functional,uniform, and macroporous latex particles: Preparation,electron microscopic characterization,and nonspecific protein adsorption properties

A series of uniform, macroporous particles with different surface chemistries were prepared with different acrylic comonomers [methyl methacrylate (MMA), butyl methacrylate (BMA), epoxypropyl methacrylate (EPMA), 2‐hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA)] with styrene–divinylbenzene (S–DVB) in a multistep seeded polymerization. In the synthesis, uniform polystyrene seed particles 6.2 μm in size were swollen first with a low molecular weight organic agent and then with a monomer phase including an S–DVB mixture and a relatively polar acrylic monomer. Final macroporous particles approximately 10 μm in size were obtained by the repolymerization of the monomer phase in the swollen seed particles. Surface and bulk morphologies were investigated with scanning and transmission electron microscopy, respectively. Although highly porous particles could be achieved with relatively hydrophobic monomers such as styrene, BMA, MMA, and EPMA, the use of hydrophilic monomers such as HEMA and MAA led to the synthesis of uniform particles with lower macroporosity. A comparison of Fourier transform infrared and Fourier transform infrared/diffuse reflectance spectroscopy spectra indicated that the concentration of polar acrylic monomer on the surface was higher than in the bulk structure. The nonspecific protein adsorption behavior of uniform, macroporous particles was investigated with albumin as a model protein. The highest nonspecific albumin adsorption was observed with plain poly(styrene‐co‐divinylbenzene) [poly(S–DVB)] particles. The particles produced with MMA and EPMA also exhibited albumin adsorption capacities very close to that of plain poly(S–DVB). Reasonably low nonspecific albumin adsorption was observed with the particles produced in the presence of MAA, HEMA, and BMA. Poly(S–DVB) particles functionalized with poly(vinyl alcohol) provided nearly zero nonspecific albumin adsorption. For nonspecific albumin binding onto the particles via a physical adsorption mechanism, desorption ratios higher than 80% could be achieved. The desorption ratio with the EPMA‐carrying particles was only 5% because the albumin adsorption onto EPMA‐carrying particles occurred predominantly with covalent‐bond formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 414–429, 2002; DOI 10.1002/app.10412     

乳液法聚苯乙烯纳米微球的制备

采用十二烷基硫酸钠为乳化剂、过硫酸盐为引发剂、苯乙烯为单体,在低水油比的条件下,采用乳液聚合方法合成了聚苯乙烯纳米微球,探讨了乳化剂用量、乳化时间、反应温度、引发剂用量和反应时间对单体转化率及产物分子量的影响.结果表明:在低水油比条件下,反应参数对苯乙烯的转化率和聚苯乙烯的分子量具有一定的影响.在最优条件下苯乙烯的转化率达到98%、聚苯乙烯的分子量达到32万.激光粒度分布测试结果显示,所得产物为单分散纳米微球.     

Atomic force microscopy characterization of ultrathin polystyrene films formed by admicellar polymerization on silica disks

Atomic force microscopy was used to study the characteristics of polymer films formed via admicellar polymerization (the polymerization of monomers solubilized in adsorbed surfactant aggregates). The investigated system included cetyltrimethylammonium bromide (C₁₆TAB) as a cationic surfactant, styrene, 2,2′‐azobisisobutyrilnitrile as an initiator, and polished silica disk substrates. Our goal was to examine changes in the properties and morphology of the formed polymer films due to changes in the surfactant and monomer feed levels. Normal tapping and phase‐contrast modes in air were used to image the nanoscopic and microscopic morphologies of the polystyrene‐modified silica. The root‐mean‐square roughness of the surface before and after modification was statistically analyzed and compared. The images were captured with loading‐force set‐point ratios of 0.2–0.9, and this allowed us to examine the stability of the polystyrene films. In the first series, for which the feed ratio of C₁₆TAB to styrene was kept constant and the total feed concentration was varied, a uniform layer of a polystyrene film was observed along with some nanometer‐size aggregates at high feed concentrations of both C₁₆TAB and styrene. These droplets eventually agglomerated with the film beneath and formed larger macrodroplets in a ring arrangement. At lower concentrations, droplets and holes were observed that eventually agglomerated to form a bicontinuous thin film. In the second experimental series, the concentration of C₁₆TAB was kept constant, and the feed ratio of C₁₆TAB to styrene was varied. A smooth thin film was observed at high concentrations of styrene. This film could be deformed and/or removed to expose the silica surface beneath. At lower styrene loadings, the polystyrene film became unstable and formed dropletlike aggregates, possibly because of either the uneven adsolubilization of the styrene monomer within the admicelle or the dewetting effect during washing and drying. The structure of the polystyrene film formed on a smooth silica disk was very dependent on the amount of the surfactant fed to the system; this contrasted with the results on precipitated silica. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 36–46, 2003     

Syntheses of acrylate core/shell imbiber beads by seeded suspension copolymerization and one‐stage copolymerization for solvent absorption–desorption

Seeded suspension copolymerization or a one‐stage copolymerization was used to synthesize acrylate core/shell imbiber beads. A two‐stage polymerization technique was used for seeded suspension polymerization. The seed particles for poly(methyl acrylate) or poly(2‐ethylhexyl acrylate) were synthesized first in a mixed solvent of toluene/isooctane containing the ethylene glycol dimethacrylate (EGDMA) crosslinking agent. These beads were swollen in styrene‐EGDMA‐BPO (benzoyl peroxide) and then polymerized in the aqueous phase to produce the polystyrene (PS) shell. The one‐stage copolymerization was carried out in toluene/isooctane containing methyl methacrylate (MMA), styrene (St), EGDMA, and BPO at 75°C for 10 h to give a core/shell copolymer of St‐MMA morphology. The appearance of core/shell imbiber beads prepared from these two techniques varied from monomer to monomer. This article describes the preparation, characterization, and application of the core/shell beads for organic solvent absorption/desorption. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 670–682, 2002     

Preparation of macroporous,monodisperse, functionalized styrene–divinylbenzene copolymer beads: Effect of the nature of the monomers and total porogen volume on the porous properties

The staged templated suspension polymerization method was used for the preparation of 5 μm beads from mixtures of styrene and several substituted styrene monomers, including 4-methylstyrene, 4-aminostyrene, 3-aminostyrene, 4-acetoxystyrene, and 4-tert-butoxycarbonyl oxystyrene, with divinylbenzene in the presence of various amounts of linear polystyrene and dibutyl phthalate as porogens. The nature of the monomer as well as the total percentage of porogenic compounds in the polymerization mixture have a large effect on the porous properties and surface morphology of the monodisperse beads. Beads with large pores can only be obtained once the percentage of porogen in the mixture exceeds a threshold value that varies with the type of monomers involved in the polymerization. The level of incompatibility of the functional polymer chains formed during the crosslinking polymerization with the linear polystyrene porogen that is present in the polymerization mixture is another variable that also affects both the porous properties and the morphology of the beads. Because better compatibility is achieved, this effect is less pronounced if unfunctionalized styrene is used as a monomer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 597–607, 1998     

Modeling and experimental studies on single particle coal devolatilization and residual char combustion in fluidized bed

Single particle devolatilization followed by combustion of the residual coal char particle has been analyzed in a batch-fluidized bed. The kinetic scheme with distributed activation energy is used for coal devolatilization while multiple chemical reactions with volume reaction mechanism are considered for residual char combustion. Both the models couple kinetics with heat transfer. Finite Volume Method (FVM) is employed to solve fully transient partial differential equations coupled with reaction kinetics. The devolatilization model is used to predict the devolatilization time along with residual mass and particle temperature, while the combined devolatilization and char combustion model is used to predict the overall mass loss and temperature profile of coal. The computed results are compared with the experimental results of the present authors for combustion of Indian sub-bituminous coal (15% ash) in a fluidized bed combustor as well as with published experimental results for coal with low ash high volatile matter. The effects of various operating parameters like bed temperature, oxygen mole fraction in bulk phase on devolatilization time and burn-out time of coal particle in bubbling fluidized bed have been examined through simulation.     

Benzocyclobutenes as styrene monomer scavengers and molecular weight “stabilizers” in atactic and syndiotactic polystyrenes

Syndiotactic polystyrene (SPS) is a semicrystalline polymer with a melting point of 270°C. At processing temperatures of 300°C or higher, SPS begins to decompose with loss of molecular weight and the formation of styrene monomer. Under these conditions, atactic polystyrene also decomposes. One approach to controlling this generation and buildup of styrene and the molecular weight loss during processing is to add a compound that will react with styrene and/or with the polymer decomposition products at the processing conditions. This report describes the use of three benzocyclobutene (BCB) compounds (ethylene bis‐BCB, divinyl disiloxane bis‐BCB, and a copolymer of styrene and 4‐vinyl BCB) during SPS and atactic polystyrene processing. The conclusions are: 1. BCB moieties, when extruded with SPS at the 2 wt % level, caused a substantial decrease in residual styrene compared with a control SPS; 2. BCB compounds, when extruded with SPS, resulted in high molecular weight fractions. The result with the divinyl disiloxane bis‐BCB was especially dramatic; and 3. BCB functionalized materials may find utility as additives in SPS during processing to minimize loss of molecular weight and buildup of styrene. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2008–2015, 2000     

我国苯乙烯与聚苯乙烯市场分析

我国苯乙烯与聚苯乙烯自给率一直较低,近几年逐渐上升,国产聚苯乙烯与国外产品、合资企业产品相比处于绝对劣势,国内的聚苯乙烯行业要想发展要独辟蹊径。