Maghnite‐H+ as a cationic catalyst in the synthesis of poly(1,3‐dioxolane) and α,ω‐methacryloyloxy‐poly(1,3‐dioxolane)

The polymerization of 1,3‐dioxolane catalyzed by Maghnite‐H^+; (Mag‐H⁺), a montmorillonite sheet silicate clay exchanged with protons, was investigated. The cationic ring‐opening polymerization of 1,3‐dioxolane was initiated by Mag‐H⁺ at different temperatures (20, 30, 50, and 70°C) in bulk and in a solvent (dichloromethane). The effects of the amount of Mag‐H⁺ and the temperature were studied. The polymerization rate and the average molecular weights increased with an increase in the temperature and the proportion of the catalyst. These results indicated the cationic nature of the polymerization and suggested that the polymerization was initiated by proton addition to the monomer from Mag‐H⁺. Moreover, we used a simple method, in one step in bulk and in solution at room temperature (20°C), to prepare a telechelic bismacromonomer: α,ω‐bisunsaturated poly(1,3‐dioxolane). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 78–82, 2006     

Synthesis and structure of the poly(methyl methacrylate) microlatex

Microemulsion polymerization is a new approach for preparing nanosize polymer materials. In this article, a nanosize poly(methyl methacrylate) (PMMA) was prepared by a novel microemulsion polymerization. The kinetics of the polymerization and the effects of the temperature, the monomer, and emulsifier/water ratio on the polymerization were investigated by means of the conversion, the transmittance, and the refractive index measurements. The structure of the obtained PMMA microlatex was studied through transmission electron microscopy (TEM), nuclear magnetic resonance (¹H‐NMR), and differential scanning calorimetry (DSC). The results show that the polymerization exhibits typical kinetic characteristics of a microemulsion polymerization, i.e., there only exists two rate stages: a stage of increasing rate, and a stage of decreasing rate, and no constant rate stage is observed during the polymerization. The obtained PMMA microparticles are very uniform, regular, and small, being about 17–33 nm in the number‐average diameter. The polymer has higher molecular weight (1.71 × 10⁶ viscosity average molecular weight), higher tacticity (51% syndiotacticity), and higher glass transition temperature (127°C), much different from the commercial PMMA. Experimentally, a stable and transparent PMMA microlatex with higher polymer content (30–40 wt %), lower weight ratio of emulsifier to water (E/W ≤ 0.03) and emulsifier to monomer (E/M ≤ 0.05) as well as smaller particle size (d_p < 40 nm), has been prepared, which is very important for the industrialization of the microemulsion polymerization technique. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2839–2844, 2002     

Control of molecular weight distribution for polypropylene obtained by commercial Ziegler–Natta catalyst: effect of temperature

Polymerization of propylene was carried out by using MgCl₂-supported TiCl₄ catalyst in conjunction with triethylaluminium (TEA) as cocatalyst. The effect of polymerization temperature on polymerization of propylene was investigated. The catalyst activity was influenced by the polymerization temperature significantly and the maximum activity of the catalyst was obtained at 40 °C. With increasing the polymerization temperature, the molecular weight of polypropylene (PP) drastically decreased, while the polydispersity index (PDI) increased. The effect of the two-stepwise polymerization procedure on the molecular weight and molecular weight distribution of PP was studied and the broad PDI of PP was obtained. It was also found that the PDI of PP could be controlled for propylene polymerization through regulation of polymerization temperature. Among the whole experimental cases, the M _w of PP was controlled from 14.5 × 10⁴ to 75.2 × 10⁴ g/mol and the PDI could be controlled from 4.7 to 10.2.     

Synthesis and characterization of polyacrylonitrile pregelled starch graft copolymers using ferrous sulfate‐hydrogen peroxide redox initiation system as surface sizing agent

A graft copolymer was synthesized by graft copolymerization of starch with styrene (St) and butyl acrylate (BA), using ferrous sulfate‐hydrogen peroxide redox initiation system. The starch was pregelled in the presence of acrylonitrile (AN) in aqueous alkali at high temperature before graft polymerization. Major factors affecting the polymerization reaction were investigated. It was found that a graft copolymer with higher percentage conversion (PC), graft efficiency (GE) and graft percentage (GP) was obtained by controlling the initiator concentration, concentration, and ratio of monomers and polymerization temperature. The optimum conditions were as follows: H₂O₂ concentration, 12%; monomer concentration, 120%; St/BA ratio, 1 : 1; polymerization temperature, 65°C. Fourier transform infrared spectroscopy and NMR analyses were used to gain information on the structure of the products. It was demonstrated that St, BA, and AN had been successfully grafted onto starch and ? CN had been saponified into ? CONH₂ and ? COO^? to a certain degree when pregelling. Scanning electron microscope micrographs showed the coarse structure and broad network. The graft polymerization took place on the surface of starch granule and led to amorphization of the starch structure. Graft polymer had better thermal stability and was endowed with pseudo‐plasticity. It was observed that the starch graft copolymer offers good properties such as water resistance as surface‐sizing agent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Emulsion polymerization of tetrafluoroethylene: effects of reaction conditions on the polymerization rate and polymer molecular weight

The emulsion polymerization of tetrafluoroethylene (TFE) was carried out in a semibatch reactor using a chemical initiator (ammonium persulfate) and a fluorinated surfactant (FC-143). The effects of the reaction condition were investigated though the polymerization rate, molecular weight of polytetrafluoroethylene (PTFE), and stability of the dispersion. The emulsion polymerization of TFE was different from conventional emulsion polymerization. The polymerization rate was suppressed when the polymer particles were significantly coagulated. The polymerization rate increased with operating temperature, surfactant concentration, and agitation speed, due to the enhanced stability of the polymer particles. However, once the parameter value was reached, the rate decreased due to the coagulation of the particles. Stable PTFE dispersion particles were obtained when the surfactant concentration was in the range between 3.48 × 10⁻³ and 32.48 × 10⁻³ mol/liter, which is below critical micelle concentration (CMC). The molecular weight of the PTFE obtained was a function of the surfactant and initiator concentrations, and the polymerization temperature. The molecular weight increased as each parameter decreased. This is against the phenomena observed in a conventional emulsion polymerization. A stable PTFE dispersion polymer having a high molecular weight was obtained by optimizing the reaction conditions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 777–793, 1999     

CuBr2/Me6TREN-mediated living radical polymerization of methyl methacrylate at ambient temperature

A universal nitrogen based ligand, tris[2-(dimethylamino) ethyl] amine (Me₆TREN), was firstly employed as both reducing agent and ligand for atom transfer radical polymerization with activators regenerated by electron transfer (ARGET ATRP) of methyl methacrylate (MMA) in bulk and solution, using CuBr₂ as the catalyst and 2-bromoisobutyrate as the initiator. Remarkably high activity catalytic system (CuBr₂/Me₆TREN) enabled the ambient temperature polymerization and thus biradical termination reactions were low. The polymerization exhibited typical living radical polymerization features, including pseudo first-order kinetics of polymerization, linear increase in the molecular weight versus monomer conversion, and low polydispersity index values. Moreover, effects of solvent and reaction temperature on the polymerization were investigated in detail. The rate of polymerization increased with reaction temperature and the apparent activation energy of the polymerization was calculated to be 51.11 kJ/mol. Gel permeation chromatography and ¹H NMR analyses as well as chain extension experiment confirmed the living chain-end functionality.     

Interpenetrating polymer network of poly(vinyl chloride) and polymethacrylates

A curable polymeric composite was prepared using equal weights of poly(vinyl chloride) (PVC), reactive polyfunctional methacrylate monomers, and inorganic fillers. Peroxide initiated in situ polymerization of the polyfunctional methacrylate monomers in the PVC matrix produced an interpenetrating polymer network (IPN) structure. The polymerization kinetics and the degree of polymerization were investigated using differential scanning calorimetry (DSC), carbon-13 nuclear magnetic resonance (¹³C NMR), and solvent extraction. All measurements indicated that during polymerization, the PVC is either crosslinked by or grafted onto the methacrylate three-dimensional network structure. The rheological properties of the composite were measured before curing using a Rheometrics mechanical spectrometer and found to exhibit mainly viscous behavior and diminished elasticity. The PVC and the methacrylate monomers form a two-phase system when mixed at room temperature. However, when heated to 100°C the PVC dissolves in the monomers and forms a one-phase optically clear blend with a single glass transition temperature. In the presence of peroxide, the one-phase blend is stable and does not separate out upon cooling and storing at room temperature.     

Grafting of acrylic monomers onto cotton fabric using an activated cellulose thiocarbonate–azobisisobutyronitrile redox system

The feasibility of a cellulose thiocarbonate–azobisisobutyronitrile (AIBN) initiation system to induce graft copolymerization of methyl methacrylate (MMA) and other acrylic monomers onto cotton fabric was investigated. Other acrylic monomers were acrylic acid, acrylonitrile, and methyl acrylate. The initiation system under investigation was highly activated in the presence of a metal‐ion reductant or a metal‐ion oxidant in the polymerization medium. A number of variables in the grafting reaction were studied, including AIBN concentration, pH of the polymerization medium, nature of substrate, monomer concentration, duration and temperature of polymerization, and composition of the solvent/water polymerization medium. The solvents used were methanol, isopropanol, 1,4‐dioxane, cyclohexane, benzene, dimethyl formamide, and dimethyl sulfoxide. There were optimal concentrations of AIBN (5 mmol/L), MMA (8%), Fe²⁺ (0.1 mmol/L), Mn²⁺ (8 mmol/L), and Fe³⁺ (2 mmol/L). A polymerization medium of pH 2 and temperature of 70°C constituted the optimal conditions for grafting. The methanol/water mixture constituted the most favorable reaction medium for grafting MMA onto cotton fabric by using the Fe²⁺–cellulose thiocarbonate–AIBN redox system. MMA was superior to other monomers for grafting. The unmodified cotton cellulose showed very little tendency to be grafted with MMA compared with the chemically modified cellulosic substrate. A tentative mechanism for the grafting reaction was proposed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1261–1274, 2004     

Maghnite-H, an ecocatalyst for cationic polymerization of N-vinyl-2-pyrrolidone

The polymerization of N-vinyl-2-pyrrolidone catalyzed by the Maghnite-H⁺ (Mag-H) was investigated. Mag-H is a montmorillonite sheet silicate clay, exchanged with protons. It was found that the cationic polymerization of N-vinyl-2-pyrrolidone (NVP) is initiated by Mag-H at 30 °C in bulk and in solution. The effect of the amount of Mag-H, the temperature and the solvent was studied. The polymerization rate increased with increase in the temperature and the proportion of catalyst, and it was larger in nitrobenzene than that in toluene. These results indicated the cationic nature of the polymerization. It may be suggested that the polymerization is initiated by proton addition to monomer from Mag-H.     

Preparation of high molecular weight poly(N‐vinylcarbazole) in high yield by low‐temperature precipitation polymerization of N‐vinylcarbazole

To produce high molecular weight poly(N‐vinylcarbazole) (PVCZ) with high conversion, N‐vinylcarbazole (VCZ) was heterogeneously polymerized in methanol at 30, 40 and 50 °C using a low temperature initiator, 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN), and the effects of polymerization temperature and concentration of initiator and solvent on the polymerization behaviour and molecular parameters of PVCZ investigated. Globally, experimental results correspond to predicted ones. Low polymerization temperature using ADMVN and a heterogeneous system using methanol proved to be successful in obtaining poly(N‐vinylcarbazole) (PVCZ) of high molecular weight and high conversion with small temperature rise during polymerization, although free radical polymerization by azoinitiator was used. The polymerization rate of VCZ in methanol at 30 °C is proportional to the 0.88th power of ADMVN concentration. The molecular weight is higher and the molecular weight distribution is narrower with PVCZ polymerized at lower temperatures. For PVCZ produced in methanol at 30 °C using an ADMVN concentration of 0.0001 mol/mol of VCZ, a weight average molecular weight of 1 750 000 g mol⁻¹ is obtained, with a polydispersity index of 1.82 © 2000 Society of Chemical Industry     

Graft copolymerization of methyl methacrylate and other vinyl monomers onto cotton fabric using ferrous cellulose thiocarbonate–N-bromosuccinimide redox initiation system

The cellulose thiocarbonate, in the fabric from, was treated first with a freshly prepared ferrous ammonium sulphate (FAS) solution. The sotreated fabric formed, with N-bromosuccinimide (NBS), an effective redox system capable of initiating grafting of methyl methacrylate (MMA) and other vinyl monomers onto the cotton fabric. The effect of the polymerization conditions the polymer criteria, namely, graft yeild, homopolymer, total conversion, and grafting efficiency, was studied. These polymer criteria were found to depend extensively upon concentrations of the Fe²⁺ ion (activator), NBS (initiator), and MMA; pH of the polymerization medium, and duration and temperature of polymerization. Based on detailed investigation of these factors, the optimal conditions for grafting were as follows: Fe²⁺, 1 × 10⁻³ mol/L; NBS, 1 × 10⁻² mol/L; MMA, 4%; pH, 2: polymerization time, 150 min; polymerization temperature, 60°C; material/liquor ratio, 1: 100. Under these optimal conditions, the rates of grafting of different vinyl monomers were in the following sequence: methyl methacrylate ≫ methyl acrylate > acrylonitrile. Other vinyl monomers namely, acrylic acid, and methacrylic acid have no ability to be grafted to the cellulosic fabric using the said redox system. A tentative mechanism for the polymerization reaction is suggested. © 1996 John Wiley & Sons, Inc.     

Synthesis of an organic semiconductor by polimerization of 3-amino-1,2,4-triazole

We performed the polymerization of 3-amino-1,2,4-triazole (ATA), an insulator material, in acidic aqueous solution with ammonium persulfate, as oxidant agent. The new material, conveniently doped, turned out to be a semiconductor tetramer. The characterization was carried out using physical and spectroscopic techniques (elemental analysis, infrared spectroscopy, ¹H NMR, ¹³C NMR and mass spectra). Thermogravimetric analysis (TGA) indicated that this oligomer enhances thermal stability of starting material. The room temperature electrical conductivity of the synthesized oligomer (OATA) was 3.1 × 10⁻⁴ S cm⁻¹.The kinetic polymerization was analyzed by UV–vis spectroscopy, taking into account the pH dependence, monomer–oxidant ratio and monomer concentration. A possible polymerization mechanism was proposed.     

Synthesis,structure, and properties of syndiotactic polystyrene catalyzed by Cp*Ti(OBz)3/MAO/TIBA

The synthesis of syndiotactic polystyrene (sPS) catalyzed with Cp*Ti(OBz)₃/MAO/TIBA and toluene as the solvent and the effects of polymerization temperature and the external addition of TIBA on polymerization behavior were investigated. The study revealed that catalytic activity increased with polymerization temperature. The greatest activity, 619 kg sPS mol^?1 Ti h^?1, was exhibited up to 90°C. TIBA also improved catalytic activity. The molecular weight of the polymer obtained decreased with polymerization temperature and the amount of TIBA. The structure and properties of syndiotactic polystyrene were characterized by ¹³C‐NMR, FTIR, DSC, and GPC methods. It was confirmed that the sPS obtained featured all‐trans planar zigzag conformation and higher syndiotacticity, molecular weight, and melting point. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 501–505, 2007     

The structural transformation during polymerization of benzoxazine/FeCl3 and the effect on the thermal stability

The mixture of bisphenol A/aniline-based benzoxazine (BA-a) and FeCl₃ was prepared at 40 °C and then was cured to get the polymer at elevated temperatures. The thermal stability of the modified polybenzoxazine was improved and its char yield at 800 °C increased by 11%. The reason for the improvement of the thermal stability and the structural transformation during polymerization was systematically investigated by Fourier transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance spectroscopy (¹H NMR), thermo-gravimetric analysis (TGA), pyrolysis-gas chromatography/mass spectrometry (Py/GC–MS), TGA-IR and element analysis (EA). The results show that BA-a can partially undergo the ring-opening polymerization at a low temperature in the presence of FeCl₃ and generate some oligomers containing N, O-acetal-type bridge structures. At a high temperature, this structure can be transformed into the arylamine Mannich bridge structure which can delay degradation of the aniline moiety. Besides, the volatilization of fragmented Schiff base structures can be found during cure and more thermostable crosslinked structures are formed in polybenzoxazine. The entire polymerization mechanism of BA-a with FeCl₃ was proposed.     

Effects of reaction conditions on laccase‐catalyzed α‐naphthol polymerization

Enzymatic oxidative polymerization of α‐naphthol was carried out batch‐wise with the laccase enzyme, produced by Trametes versicolor (ATCC 200801). The polymerization reaction was conducted in a closed, temperature controlled system containing acetone (solvent) and sodium acetate buffer for pH control. The effects of the organic solvent (acetone) composition, monomer (α‐naphthol) and enzyme concentrations, buffer pH and temperature on the polymerization rate were investigated with respect to initial reaction conditions and depletion rate of dissolved oxygen. The optimum acetone composition, pH, monomer, dissolved oxygen and enzyme concentrations were determined as 50% (v/v), 5, 3409 gm⁻³, 20.3 gm⁻³ and 0.173 U cm⁻³, respectively; these values provided the most desirable conditions for initial reaction rate. Temperature rise supported the rate increase up to 37 °C, after which the rate tended to be stable due to a drop in dissolved oxygen concentration. The product polymer, poly(α‐naphthol), with an average molecular weight of 4920 Da was soluble in common organic solvents. © 2000 Society of Chemical Industry     

Organic/inorganic support for immobilizing (n‐BuCp)2ZrCl2/TiCl3 hybrid catalyst for use in the preparation of polymer blends

Reactor blends of ultrahigh‐molecular‐weight polyethylene (UHMWPE) and low‐molecular‐weight polyethylene (LMWPE) were synthesized by two‐step polymerization using a hybrid catalyst. To prepare the hybrid catalyst, styrene acrylic copolymer (PSA) was first coated onto SiO₂/MgCl₂‐supported TiCl₃; then, (n‐BuCp)₂ZrCl₂ was immobilized onto the exterior PSA. UHMWPE was produced in the first polymerization stage with the presence of 1‐hexene and modified methylaluminoxane (MMAO), and the LMWPE was prepared with the presence of hydrogen and triethylaluminium in the second polymerization stage. The activity of the hybrid catalyst was considerable (6.5 × 10⁶ g PE (mol Zr)^?1 h^?1), and was maintained for longer than 8 h during the two‐step polymerization. The barrier property of PSA to the co‐catalyst was verified using ethylene polymerization experiments. The appearance of a lag phase in the kinetic curve during the first‐stage polymerization implied that the exterior catalyst ((n‐BuCp)₂ZrCl₂) could be activated prior to the interior catalyst (M‐1). Furthermore, the melting temperature, crystallinity, degree of branching, molecular weight and molecular‐weight distribution of polyethylene obtained at various polymerization times showed that the M‐1 catalyst began to be activated by MMAO after 40 min of the reaction. The activation of M‐1 catalyst led to a decrease in the molecular weight of UHMWPE. Finally, the thermal behaviors of polyethylene blends were investigated using differential scanning calorimetry. Copyright © 2011 Society of Chemical Industry     

Co γ-irradiation-initiated RAFT polymerization of VAc at room temperature

In this work, the reversible addition-fragmentation chain transfer (RAFT) polymerization of vinyl acetate (VAc) was successfully performed at room temperature using ⁶⁰Co γ-irradiation as the initiation source. Under the dose rate of 10 Gy/min irradiation, the polymerization proceeded smoothly and converted approximately 90% of the monomer within 7 h. The molecular weight distribution (M_w/M_n) remained narrow (M_w/M_n < 1.35) up to 90% conversion. Compared to AIBN-initiated RAFT polymerization at 60 °C, ⁶⁰Co γ-irradiation-initiated RAFT polymerization is a technique that can better control the molecular weight, especially at high conversion. The ¹H NMR spectra and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry confirmed that most of the chain ends of poly(VAc) (PVAc) from γ-irradiated RAFT polymerization were living and can be reactivated for chain-extension reactions. The microstructures of PVAc from ⁶⁰Co γ-irradiated RAFT polymerization (almost head-to-tail addition) and AIBN-initiated RAFT polymerization (5% tail-to-tail addition) were different, as revealed by the ¹³C NMR spectra. For the first time, ⁶⁰Co γ-irradiation was used as an initiation source for RAFT polymerization of VAc at room temperature.     

Synthesis, characterization, and thermally activated polymerization behavior of bisphenol-S/aniline based benzoxazine

A difunctional benzoxazine monomer, 6,6′-bis(3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazinyl) sulfone (BS-a), was synthesized via a solution method from bisphenol-S, aniline and formaldehyde. The chemical structure of the benzoxazine was confirmed by ¹H and ¹³C nuclear magnetic resonance spectroscopy, Fourier transform infrared (FTIR) spectroscopy, elemental analysis, and size exclusion chromatography. The ring-opening polymerization of BS-a monomer was investigated with FTIR under air and nitrogen atmospheres, and with differential scanning calorimetry (DSC) in both dynamic and isothermal conditions. The FTIR results show that the absorption intensities of C-O-C, C-N-C, and oxazine ring decrease gradually with temperature and time rising during the polymerization reaction. The change rates of some absorption intensities of oxazine ring are affected by different atmospheric environments, and a higher degree of conversion is obtained in nitrogen than that in air at the same reaction temperature and in equal time. Kinetic parameters of the dynamic polymerization DSC results were evaluated with Kissinger and Ozawa methods, respectively. The isothermal DSC results show that the polymerization reaction of BS-a monomer follows an autocatalytic mechanism.     

Cationic polymerization of styrene by the TiCl4/N,N,N′,N′-tetramethylethylenediamine(TMEDA) catalyst system in benzotrifluoride,an environmentally benign solvent,at room temperature

Highly efficient carbocationic polymerization of styrene was achieved under environmentally advantageous conditions in benzotrifluoride, BTF (α,α,α-trifluorotoluene, TFT), an environmentally benign solvent at room temperature, that is without any energy consumption for cooling or heating, with even better yields than that in the usually applied volatile and harmful, widely used chlorinated solvent, dichloromethane (DCM). The polymerization was initiated by 1-phenylethyl chloride in conjunction with the TiCl₄/TMEDA (N,N,N′,N′-tetramethylethylenediamine) catalyst (coinitiator) system. Within a very short reaction time (5 min), higher conversion values were obtained in BTF (89%) than in DCM (76%), that is the TiCl₄/TMEDA combination proved to be a powerful catalyst for the carbocationic polymerization of styrene even in BTF. The molecular weight distributions of the synthesized polymers were relatively narrow in both solvents (M_w/M_n = 1.29–1.65). The effect of the increasing reaction temperature (up to room temperature) was also investigated. With increasing reaction temperature, the polydispersity decreased and M_n close to the theoretical one was obtained in BTF at room temperature. Structural analysis with ¹H NMR revealed that the major chain breaking reaction in this polymerization is indanyl ring formation between the penultimate monomer unit and the propagating carbocation. These results indicate that BTF can be utilized as a unique, inert, non-volatile, environment friendly solvent with medium polarity for cationic polymerization of styrene, a nonfluorous monomer, and based on these results, presumably it may be also applied effectively as a quite universal solvent for a large array of various polymerizations and copolymerizations for not only fluorinated, but also for nonflourous monomers, and other chemical reactions as well.     

Blends of poly(hydroxyether of bisphenol A) and polycarbonate: in situ polymerization preparation,miscibility, and transreaction

In the presence of polycarbonate (PC), the polymerization of diglycidyl ether of bisphenol A (DGEBA) and bisphenol A in the melt was initiated to prepare blends of poly(hydroxyether of bisphenol A) (phenoxy) and PC. The polymerization reaction started from the initially homogeneous ternary mixture consisting of DGEBA, bisphenol A, and PC; phenoxy/PC blends with PC content up to 20 wt % were obtained. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were employed to characterize the miscibility of the as-polymerized blends. All the blends displayed separate glass transition temperatures (T_g's), that is, the blends were phase-separated. The formation of a two-phase structure is considered to result from phase separation induced by polymerization. This result is consistent with the immiscibility established through solution- and melt-blending approaches. The insolubility of the as-polymerized blends showed that crosslinking between the components occurred. Both Fourier-transform infrared (FTIR) and solid ¹³C-nuclear magnetic resonance (¹³C-NMR) spectroscopic studies demonstrated a transreaction between the components and in situ polymerization of DGEBA and bisphenol A in the presence of PC, which yielded a phase-separated, transreacted material. The results of this work provide a contrast to those of the transreacted phenoxy/PC blends based on conventional blending methods; however, the transreaction in the present case occurred at a much lower temperature (180^oC), at which polymerization blending was carried out. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1181–1190, 1999