Development and characterization of reactively extruded PVC/polystyrene blends

PVC/PS blends are obtained through a reactive extrusion–polymerization method by the absorption of a solution of styrene monomer, initiator, and a crosslinking agent in commercial suspension‐type porous polyvinyl chloride (PVC) particles, forming a dry‐blend with a relatively high monomer content. These PVC/styrene dry‐blends are reactively polymerized in a twin‐screw extruder in the melt state. They do not contain monomer residues as detected by GC. The transparency, fracture surface morphology, thermal stability, rheology and static and dynamic mechanical properties of these blends are compared to physical PVC/PS blends at similar compositions. Owing to the high polymerization temperature (180°C), short PS chains are formed in the reactive extrusion process. These short chains are dispersed both as a separate phase of ～2 μm particles (recognized by SEM) and also as molecularly dispersed chains enhancing plasticization and compatibilization. The molecularly dispersed short PS chains tend to plasticize the PVC phase, reducing its melt viscosity and glass transition temperature. The content of the short PS chains forming the dispersed separate PS particles is too low for DMTA to detect a separate T_g. Thus, reactively extruded PVC/PS blends exhibit single T_g transitions at lower temperatures compared with the neat PVC. Migration of the PVC's low‐molecular‐weight additives (lubricants and thermal stabilizer) to the PS phase is observed in the physical PVC/PS blends, causing antiplasticization of the PS phase. This results in both reduction of the T_g and an increase in the thermal stability of the PS phase in the physical PVC/PS blends. Comparing TGA thermograms of reactively extruded and physical PVC/PS indicates that the PS formed in the extruder is different from the commercial PS. This can stem from various chemical reactions that can take place in the studied reactive polymerization process. Polym. Eng. Sci. 44:1473–1483, 2004. © 2004 Society of Plastics Engineers.     

Syndiotactic polymerization of styrene: Study of catalyst components and polymerization conditions

Syndiotactic polystyrene (s‐PS) was prepared using monotitanocene catalyst of cyclopentadienyl titanium trichloride (CpTiCl₃) activated by methylaluminoxane (MAO). Solution polymerization was carried out in toluene using different polymerization conditions. Syndiotacticity index (SI) between 68 and 91.6% was obtained. Increasing Al/Ti molar ratio shows an increase in both conversion percentage and SI. The conversion increased linearly with increasing Al/Ti molar ratio in the range studied. The conversion reached to an optimum value of about 65% at styrene/Al molar ratio of 2.83, while no regular behavior of SI was observed with changing the ratio. Effect of temperature of the range 50–80°C on polymerization was studied. The most favorable temperature for the polymerization regarding activity is 70°C; however SI decreased with temperature up to 80°C. H₂ value to 140 mL/100 mL solvent increased the productivity of the catalyst, however further increase of H₂ reduced the activity of the catalyst. Polymerization time of 15 to 125 min shows a decrease in activity. The decrease was sharper for about 30 min of polymerization than longer time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2216–2221, 2006     

Ultrasonically initiated miniemulsion polymerization of styrene in the presence of Fe3O4 nanoparticles

Ultrasonically initiated miniemulsion polymerization of styrene was conducted in the presence of Fe₃O₄ nanoparticles. Stable polystyrene (PS)/Fe₃O₄ nanocomposite emulsions were prepared and magnetic PS/Fe₃O₄ composite particles were obtained through magnetic separation. The whole procedure comprised two steps. First, Fe₃O₄ nanoparticles were dispersed in the monomer phase with the aid of stabilizer Span‐80. Second, miniemulsion polymerization of styrene in the presence of Fe₃O₄ nanoparticles was carried out under an ultrasonic field in the absence of a chemical initiator. The affecting factors, including stabilizer concentration, surfactant concentration, hexadecane concentration and the amount of Fe₃O₄, were systematically studied. Stabilizer concentration, surfactant concentration and hexadecane concentration strongly affected the formation of the coagulation. The least amount of coagulation was formed at 2.5 wt% Span‐80 concentration. The addition of Fe₃O₄ nanoparticles drastically increased the polymerization rate owing to the fact that Fe₃O₄ nanoparticles increased the acoustic intensity and Fe²⁺ reacted with H₂O₂ to produce hydroxyl radicals and increase the number of radicals. The increase in cosurfactant concentration and power output also increased the polymerization rate. Copyright © 2005 Society of Chemical Industry     

Synthesis of novel magnetic polymer microspheres with amphiphilic structure

Novel magnetic polymer microspheres with amphiphilic structure ranging in diameter from 5 to 80 μm were prepared by dispersion copolymerization of styrene and poly(ethylene oxide) acrylamide macromonomer (MPEO) in the presence of Fe₃O₄ magnetic fluid. The effects of various polymerization parameters on the average particle size were systematically investigated. The average particle size was found to increase with increasing initiator concentration. It also increased with decreasing stabilizer concentration and MPEO concentration. The content of the amino groups localized in the microspheres ranged from 0.01 to 0.25 mmol/g. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1879–1884, 2003     

Ab initio reversible addition–fragmentation chain transfer emulsion polymerization of styrene/butyl acrylate mediated by poly(acrylic acid)‐block‐polystyrene trithiocarbonate

Ab initio reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of styrene/butyl acrylate was investigated with the trithiocarbonate macro‐RAFT agent poly(acrylic acid)‐block‐polystyrene (PAA‐b‐PS) as a stabilizer and a RAFT agent. Influences of the amount of ammonium persulfate (APS), the amount of PAA‐b‐PS and the mass ratio of monomers on emulsion polymerization and film properties are discussed. The particle morphology exhibited spherical‐like structure with particles of about 90 nm in diameter and relatively narrow particle size distribution characterized using transmission electron microscopy and dynamic laser scattering. Fourier transform infrared and ¹H NMR spectra showed that the styrene/butyl acrylate emulsion was successfully synthesized. The monomer conversion increased initially with increasing amount of APS, from 0.4 up to 0.8 wt%, and then decreased. The particle size increased and its distribution decreased gradually with increasing amount of APS. The monomer conversion increased from 76.83 to 94.21% as the amount of PAA‐b‐PS increased from 3 to 4 wt%, and then decreased with further increase of PAA‐b‐PS. The particle size decreased and its distribution increased with increasing amount of PAA‐b‐PS. The water resistance and solvent resistance of the polymer films initially increased and then decreased with decreasing mass ratio of butyl acrylate to styrene. © 2014 Society of Chemical Industry     

Synthesis of amphiphilic magnetic microspheres by dispersion copolymerization of styrene and poly(ethylene oxide) macromonomer

Amphiphilic magnetic microspheres ranging in diameter from 5 to 100 µm were prepared by dispersion copolymerization of styrene and poly(ethylene oxide) vinylbenzyl (PEO‐VB) macromonomer (MPEO) in the presence of Fe₃O₄ magnetic fluid. The effects of various polymerization parameters on the average particle size were systematically investigated. The average particle size was found to increase with increasing styrene concentration and initiator concentration. It also increased with decreasing stabilizer concentration and molecular weight of MPEO. The content of the hydroxyl groups localized in the microspheres ranged from 0.01 to 0.2 mmol g^?1. © 2003 Society of Chemical Industry     

Synthesis of macromonomer from radical polymerization of styrene with a polymerizable photoiniferter

α‐(Methacrylyoxylethyloxycarbonylmethyl)‐ω‐(N,N‐diethyldithiocarbamyl)polystyrene macromonomers with different molecular weights were prepared by radical polymerization of styrene (St) using β‐methacryloxylethyl 2‐N,N‐diethyldithiocarbamylacetate (MAEDCA) as a polymerizable photoiniferter in toluene under ultraviolet light. The polymerization of St with MAEDCA carried out by a “living” process; that is, both the yield and the molecular weight of the resultant polymers increased with increasing of reaction time, and the resultant polymer was a macromonomer, for example, α‐(methacrylyoxylethyloxycarbonylmethyl)‐ω‐(N,N‐diethyldithiocarbamyl)polystyrene, designated as PSt‐macromonomer. The molecular weight of the PSt‐macromonomer depended on the concentrations of the polymerizable photoiniferter and St, as well as the conversion of St. The PSt‐macromonomer can copolymerize with MMA initiated by AIBN at 65°C to form a graft copolymer (PMMA‐graft‐PSt) with PSt branches randomly distributed along the PMMA backbone. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1350–1356, 2000     

Preparation of polystyrene–clay nanocomposites via dispersion polymerization using oligomeric styrene‐montmorillonite as stabilizer

This study describes the preparation of polystyrene–clay nanocomposite (PS‐nanocomposite) colloidal particles via free‐radical polymerization in dispersion. Montmorillonite clay (MMT) was pre‐modified using different concentrations of cationic styrene oligomeric (‘PS‐cationic’), and the subsequent modified PS‐MMT was used as stabilizer in the dispersion polymerization of styrene. The main objective of this study was to use the clay platelets as fillers to improve the thermal and mechanical properties of the final PS‐nanocomposites and as steric stabilizers in dispersion polymerization after modification with PS‐cationic. The correlation between the degree of clay modification and the morphology of the colloidal PS particles was investigated. The clay platelets were found to be encapsulated inside PS latex only when the clay surface was rendered highly hydrophobic, and stable polymer latex was obtained. The morphology of PS‐nanocomposite material (after film formation) was found to range from partially exfoliated to intercalated structure depending on the percentage of PS‐MMT loading. The impact of the modified clay loading on the monomer conversion, the polymer molecular weight, the thermal stability and the thermomechanical properties of the final PS‐nanocomposites was determined. Copyright © 2012 Society of Chemical Industry     

Mechanism of particle formation in radical emulsion copolymerization of styrene with α-tert-butoxy-ω-vinylbenzyl-polyglycidol macromonomer

In the batch emulsion copolymerization of styrene and α-tert-butoxy-ω-vinylbenzyl-polyglycidol macromonomer, carried out at macromonomer concentrations exceeding the critical micelle concentration (c_mc), particles are formed by a two-step coagulative nucleation mechanism. This mechanism leaves its mark on morphology of particle interface, rate of polymerization and on molecular weight distribution of the obtained polymer. AFM studies revealed that the interface of particles is composed of objects with dimensions close to dimensions of the primary particles. Compartmentalization of styrene in the macromonomer micelles leads to the higher initial rate of styrene conversion than in the similar macromonomer free homopolymerization of styrene. The initial polymerization in the monomer-swollen macromonomer micelles, similar to the microemulsion polymerization, is responsible for the formation of the highest molecular weight component. In the mature particles there are two different polymerization loci: the interfacial layer and the core. This leads to bimodal molecular weight distribution of the formed polymer.     

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     

Controlled free radical photopolymerization of styrene initiated by trithiocarbonate

Density functional theory calculations are reported for prediction of the trends in C S bond dissociation energies and atomic spin densities for radicals using S,S′‐bis(α,α′‐dimethyl‐α‐acetic acid) trithiocarbonate (TTCA) and bis(2‐oxo‐2‐phenylethyl) trithiocarbonate (TTCB) as reversible addition fragmentation chain transfer (RAFT) reagents. The calculations predict that the value of the C S bond length (1.865 Å) of TTCA is longer than that (1.826 Å) of TTCB, and TTCA is more effective for the polymerization of styrene (St) compared to TTCB as predicted by density functional theory. In photopolymerizations, pseudo‐first‐order kinetics were confirmed for TTCB‐mediated photopolymerization of St due to the linear increase of ln([M]₀/[M]) up to about 28% conversion, suggesting the living characteristics behavior of the photopolymerization of St in the presence of TTCB. For both TTCA and TTCB the polydispersities change with increasing conversion in the range 1.10–1.45, typical for RAFT‐prepared (co)polymers and well below the theoretical lower limit of 1.50 for a normal free radical polymerization. In addition, the triblock copolymer polystyrene‐block‐poly(butyl acrylate)‐block‐polystyrene (PS PBA PS) was successfully prepared, with very good control over molecular weight and narrow polydispersity (M_w/M_n = 1.45), using PS S C(S) S PS as macro‐photoinitiator under UV irradiation at room temperature. This indicated that this reversible and valid strategy led to a better controlled block copolymer with defined structures. Copyright © 2007 Society of Chemical Industry     

Dispersion copolymerization of acrylonitrile‐vinyl acetate in supercritical carbon dioxide

Dispersion copolymerization of acrylonitrile‐vinyl acetate (AN‐VAc) had been successfully performed in supercritical carbon dioxide (ScCO₂) with 2,2‐azobisisobutyronitrile (AIBN) as a initiator and a series of lipophilic/CO₂‐philic diblock copolymers, such as poly(styrene‐r‐acrylonitrile)‐b‐poly(1,1,2,2‐tetrahydroperfluorooctyl methacrylate) (PSAN‐b‐PFOMA), as steric stabilizers. In dispersion copolymerization, poly(acrylonitrile‐r‐vinyl acetate) (PAVAc) was emulsified in ScCO₂ effectively using PSAN‐b‐PFOMA as a stabilizer. Compared with the precipitation polymerization (absence of stabilizer), the products prepared by dispersion polymerization possessed of higher yield and higher molecular weight. In addition, the particle morphology of precipitation polymerization was irregular, but the particle morphology of dispersion polymerization was uniform spherical particles. In this study, the effects of the initial concentrations of monomer and the stabilizer and the initiator, and the reaction pressure on the yield and the molecular weight and the resulting size and particle morphology of the colloidal particles were investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5640–5648, 2006     

Synthesis of poly(octadecyl acrylate‐b‐styrene‐b‐octadecyl acrylate) triblock copolymer by atom transfer radical polymerization

The synthesis of triblock copolymer poly(octadecyl acrylate‐b‐styrene‐b‐octadecyl acrylate), using atom transfer radical polymerization (ATRP), is reported. The copolymers were prepared in two steps. First, polystyrene was synthesized by ATRP using α,α′‐dichloro‐p‐xylene/CuBr/bpy as the initiating system; Second, polystyrene was further used as macroinitiator for the ATRP of octadecyl acrylate to prepare ABA triblock copolymers in the presence of FeCl₂·4H₂O/PPh₃ in toluene. Polymers with controlled molecular weight (M_n = 17,000–23,400) and low polydispersity index value (1.33–1.44) were obtained. The relationship between molecular weight versus conversion showed a straight line. The effect of reaction temperature on polymerization was also investigated, showing a faster polymerization rate under higher temperature. The copolymers were characterized by FTIR, ¹H‐NMR, DSC, and GPC and the crystallization behavior of the copolymers was also studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1539–1545, 2004     

A kinetic investigation of the in situ polymerization of methyl methacrylate under supercritical fluid CO2 conditions using high‐pressure DSC

The polymerization kinetics of methyl methacrylate (MMA) under supercritical fluid CO₂ was studied by using high‐pressure DSC. The results indicate that CO₂ can significantly reduce the cage effect and improve the chain propagation reactions, with the observed solvent‐like effects being enhanced by increased CO₂ pressures. The polymerization of MMA under isothermal conditions and 56 atm of CO₂ was characterized by a first‐order kinetic rate expression over the conversion range 20–80%. The apparent activation energy for the reaction was found to be 51.6 kJ/mol, which is less than the value reported under ambient conditions (68.2 kJ/mol). The polymerization kinetics were also evaluated under nonisothermal conditions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1236–1239, 2004     

Narrow‐disperse or monodisperse crosslinked and functional core–shell polymer particles prepared by two‐stage precipitation polymerization

Narrow‐disperse and monodisperse cross‐linked core–shell polymer particles containing different functional groups, such as esters, hydroxyls, chloromethyls, carboxylic acids, amides, cyanos, and glycidyls, in the shell layers in the micrometer size range were prepared by a two‐stage precipitation polymerization in the absence of any stabilizer. Commercial divinylbenzene (DVB), containing 80% DVB, was precipitation polymerized in acetonitrile without any stabilizer as the first‐stage polymerization and was used as the core. Several functional monomers, including methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2‐hydroxyethyl methacrylate, glycidyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, t‐butyl acrylate, i‐octyl acrylate, acrylic acid, acrylamide, acrylonitrile, styrene, and p‐chloromethyl styrene, were incorporated into the shells during the second‐stage polymerization. The resulting core–shell polymer particles were characterized with scanning electron microscopy and Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1776–1784, 2006     

Preparation and thermal property of hybrid nanocomposites by free radical copolymerization of styrene with octavinyl polyhedral oligomeric silsesquioxane

The poly(styrene‐co‐octavinyl‐polyhedral oligomeric silsesquioxane) (PS–POSS) organic–inorganic hybrid nanocomposites containing various percent of POSS were prepared via one‐step free radical polymerization and characterized by FTIR, high‐resolution ¹H NMR, ²⁹Si NMR, GPC, DSC, and TGA technologies. The POSS contents in these nanocomposites were determined using FTIR calibration curve. The result shows that the POSS contents in nanocomposites can be tailored by varying the POSS feed ratios. On the basis of the POSS contents in the nanocomposites and the ¹H NMR spectra, the number of reacted vinyl groups of each octavinyl‐POSS macromonomer were calculated to be 6–8. DSC and TGA measurements indicate that the incorporation of POSS into PS homopolymer can apparently improve the thermal properties of the polymeric materials. The dramatic T_g and T_dec increases are mainly due to the formation of star and low cross‐linking structure of the nanocomposites, where POSS cores behave as the joint points and hinder the motion and degradation of the polymeric chains. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of isopropenylbenzyl‐terminated macromonomers and preparation of polymer brushes by anionic homopolymerization

Isopropenylbenzyl‐terminated polystyrene (PS) macromonomers were synthesized by anionic addition in a two‐stage process using styrene and 1,4‐diisopropenylbenzene (DIPB) in benzene. The reaction products of polystyryl anions with DIPB provided PS macromonomer possessing less than two isopropenylbenzyl groups at the propagating end under the condition of being in hydrocarbon solvent at 25°C (ceiling temperature) because of the anionic equilibrium nature. Subsequently, anionic homopolymerization of such macromonomers was carried out in tetrahydrofuran (THF) at ?78°C using anionic initiators to prepare the polymer brushes. The conversion of polymer brushes was very low (ca. 5%). Moreover, the degree of polymerization (DP) was less than 50. The low concentration of propagating chain ends seemed to affect the formation of polymer brushes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87:1790–1793,2003     

Syndiospecific styrene polymerization with CpTiCl3/MAO: Effects of the order of reactant addition on polymerization and polymer properties

Syndiospecific styrene (St) polymerization, catalyzed by the CpTiCl₃/methylaluminoxane (MAO) system, was investigated using two different activation procedures. The polymerization parameters included polymerization time, temperature (～25–100°C), ratio of [Al]/[Ti] (～100–1000), and catalyst precursor concentration (～0.5–10.0 × 10^?4 mol Ti/L). It was found that adding reactants in the order of (CpTiCl₃ + MAO) + St (Injection of Styrene mode) gave much higher monomer conversion rates, higher weight‐average molecular weights, and narrower molecular weight distributions than for the (St + MAO) + CpTiCl₃ (Injection of Catalyst mode). The former also yielded significantly higher syndiotacticity fractions. Differential scanning calorimetry measurements showed multiple peaks exhibiting polymorphism in crystalline syndiotactic polystyrene samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1449–1455, 2004     

Dispersion polymerization of styrene in supercritical CO2 stabilized by random copolymers of 1H,1H-perfluorooctyl methacrylate and 2-dimethylaminoethyl methacrylate

The dispersion polymerizations of styrene in supercritical CO₂ employing random copolymers composed of 1,1-dihydroperfluorooctyl methacrylate (FOMA) and 2-dimethylaminoethyl methacrylate (DMAEMA) (poly(FOMA-co-DMAEMA)) as stabilizers were investigated with two different compositions. It was demonstrated that micron-sized, free-flowing, spherical polystyrene (PS) particles could be obtained in high yields by poly(FOMA-co-DMAEMA) containing as low as 50% (w/w) FOMA. Results indicate that DMAEMA units in the stabilizer, as an anchor group with its special characteristics, can be adsorbed on PS particles to provide an enough colloidal stability. The initial concentration of styrene and the stabilizer affected the molecular mass, polymerization yield, and the morphology of PS particles. The PS particles could be redispersed in buffered water (pH 2.1) by an ionic stabilization mechanism provided by DMAEMA units on the surface. Dynamic light scattering (DLS) measurements of aqueous latexes gave similar particle sizes as those from SEM analysis.     

Nitroxide‐mediated synthesis of styrenic‐based segmented and tapered block copolymers using poly(lactide)‐functionalized TEMPO macromediators

Poly(styrene)‐poly(lactide) (PS‐PLA), poly (tert‐butyl styrene)‐poly(lactide) (PtBuS‐PLA) diblocks, and poly(tert‐butyl styrene)‐poly(styrene)‐poly(lactide) (PtBuS‐PS‐PLA) segmented and tapered triblocks of controlled segment lengths were synthesized using nitroxide‐mediated controlled radical polymerization. Well‐defined PLA‐functionalized macromediators derived from hydroxyl terminated TEMPO (PLA_T) of various molecular weights mediated polymerizations of the styrenic monomers in bulk and in dimethylformamide (DMF) solution at 120–130°C. PS‐PLA and PtBuS‐PLA diblocks were characterized by narrow molecular weight distributions (polydispersity index (M_w/M_n) < 1.3) when using the PLA_T mediator with the lowest number average molecular weight M_n= 6.1 kg/mol while broader molecular weight distributions were exhibited (M_w/M_n = 1.47‐1.65) when using higher molecular weight mediators (M_n = 7.4 kg/mol and 11.3 kg/mol). Segmented PtBuS‐PS‐PLA triblocks were initiated cleanly from PtBuS‐PLA diblocks although polymerizations were very rapid with PS segments ～ 5–10 kg/mol added within 3–10 min of polymerization at 130°C in 50 wt % DMF solution. Tapering from the PtBuS to the PS segment in semibatch mode at a lower temperature of 120°C and in 50 wt % DMF solution was effective in incorporating a short random segment of PtBuS‐ran‐PS while maintaining a relatively narrow monomodal molecular weight distribution (M_w/M_n ≈ 1.5). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008