Sorption,diffusion, and permeation of ethylbenzene in poly(1‐trimethylsilyl‐1‐propyne)

The solubility, diffusivity, and permeability of ethylbenzene in poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) at 35, 45 and 55 °C were determined using kinetic gravimetric sorption and pure gas permeation methods. Ethylbenzene solubility in PTMSP was well described by the generalized dual‐mode model with χ = 0.39 ± 0.02, b = 15 ± 1, and C^′_H = 45 ± 4 cm³ (STP)/cm³ PTMSP at 35 °C. Ethylbenzene solubility increased with decreasing temperature; the enthalpy of sorption at infinite dilution was −40 ± 7 kJ/mol and was essentially equal to the enthalpy change upon condensation of pure ethylbenzene. The diffusion coefficient of ethylbenzene in PTMSP decreased with increasing concentration and decreasing temperature. Activation energies of diffusion were very low at infinite dilution and increased with increasing concentration to a maximum value of 50 ± 10 kJ/mol at the highest concentration explored. PTMSP permeability to ethylbenzene decreased with increasing concentration. The permeability estimated from solubility and diffusivity data obtained by kinetic gravimetric sorption was in good agreement with permeability determined from direct permeation experiments. Permeability after exposure to a high ethylbenzene partial pressure was significantly higher than that observed before the sample was exposed to a higher partial pressure of ethylbenzene. Nitrogen permeability coefficients were also determined from pure gas experiments. Nitrogen and ethylbenzene permeability coefficients increased with decreasing temperature, and infinite dilution activation energies of permeation for N₂ and ethylbenzene were −5.5 ± 0.5 kJ/mol and −74 ± 11 kJ/mol, respectively. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1078–1089, 2000     

Effect of pressure and temperature on chromophore reorientation in a side-chain nonlinear optical polymer

Second harmonic generation (SHG) was used to measure the temperature dependence of the reorientation activation volume of the side-chain copolymer poly(disperse red 1 methacrylate-co-methyl methacrylate) (DR1-MMA). The decay of the SHG signal from poled films of DR1-MMA was recorded at hydrostatic pressures up to 3060 atm and at different temperatures between 25°C below the glass transition temperature (T_g) to 35°C above it. The activation volume, ΔV^*, decreased with increasing temperature. The data suggests that the coupling between chromophore reorientation and the long-range motion of the polymer is stronger for the DR1-MMA side-chain system than in previously measured guest–host systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2793–2803, 1998     

Temperature dependence of the activation volume in a nonlinear optical polymer: Evidence for chromophore reorientation induced by sub-Tg relaxations

Second harmonic generation (SHG) was used to measure the temperature dependence of the reorientation activation volume of 4-(diethylamino)-4′-nitrotolane (DEANT) in poly(methyl methacrylate) (PMMA). The decay of the SHG signal from films of DEANT/PMMA was recorded at hydrostatic pressures up to 3060 atm and at different temperatures between 25°C below the glass transition temperature to 35°C above it. The activation volume, ΔV*_αβ associated with the long range α-type motion of the polymer remained constant at 213 ± 10 ų between T_g − 25°C and T_g + 10°C. At higher temperatures, ΔV*_αβ decreased linearly with increasing temperature. The activation volume, ΔV*_αβ, associated with short range secondary relaxations was constant over the entire temperature range with a value of 77 ± 10 ų. The data suggest that above T_g chromophore reorientation is coupled to both the long range and local motions of the polymer; whereas, well below T_g chromophore reorientation is closely coupled to the local relaxations of the polymer. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 901–911, 1998     

Gas permeability,diffusivity, and solubility of poly(4-vinylpyridine) film

Although poly(4-vinylpyridine) is believed to have good gas permselectivity, the intrinsic gas permeation property is rarely reported in the literature. The objective of this work is to study the the intrinsic gas permeation property of poly(4-vinylpyridine) using a free-standing film. Because of its brittleness and strong adhesion with most solid surfaces, a free-standing poly(4-vinylpyridine) film was therefore prepared from casting on a liquid mercury surface. The permeation behavior of He, H₂, O₂, N₂, CH₄, and CO₂ through the film was tested over a pressure range of 252 to 800 cm Hg at 35°C. The permeability and solubility decrease slightly with an increase in pressure, whereas the diffusivity increases as pressure increases. The pressure-dependent phenomenon can be explained using the partial immobilization model and the dual sorption model. An effective gas molecule diameter, which is defined as the square root of the product of gas collision and kinetic diameters, was used to correlate the diffusivity and gas molecule size, and an empirical equation was derived. Solubility is also a strong function of gas physical properties such as critical temperature and Lennard–Jones force constant, which are the measures of gas condensability and molecule interaction, respectively. In general, higher solubility in a polymer is obtained for gases with greater condensability and stronger interaction. Typical gas permeabilities of poly(4-vinylpyridine) measured at 619 cm Hg and 35°C are: 12.36 (He), 12.64 (H₂), 3.31 (CO₂), 0.84 (O₂), 0.14 (CH₄), and 0.13 (N₂) barrers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2851–2861, 1999     

Pressure‐temperature study of dielectric relaxation of a polyurethane elastomer

The effect of hydrostatic pressure up to 1,361 atms on the dielectric properties of a segmented polyurethane elastomer (Dow 2103‐80AE) is studied at temperatures from 0°C to 80°C. The experimental results show that the relaxation time for both the I–process, associated with the molecular motions in the hard segments, and the α–process, associated with the glass transition, increases with pressure, and this shift is more pronounced for the I–process. Besides the glass transition, it is found that the I–process can be described by the Vogel–Fulcher (V–F) and Williams–Landel–Ferry (WLF) relations. At atmospheric pressure, T_g and T₀ for the I–process are 235.9 K and 4.2 × 10³ K, respectively. Based on the V–F and WLF relations and experimental results, it is found that a parameter, C₁, in the WLF relation is independent of the pressure. Thus, a method is introduced to determine the values of both the characteristic transition temperature (T_g) and activation energy (T₀) for the processes at different pressures. As the pressure increases from atmospheric to 1,361 atms, the increase of T_g for the I–process is about 30°C. The results also show that, for both the I– and the α–processes, T₀ decreases with increasing pressure. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 983–990, 1999     

Synthesis and characterization of aromatic poly(ether ketone)s containing cyclotriphosphazene units

Bis(4-oxybenzoic acid) tetrakis(phenoxy) cyclotriphosphazene (IUPAC name: 4-[4-(carboxyphenoxy)-2,4,6,6-tetraphenoxy-1,3,5,2λ⁵,4λ⁵,6λ⁵-triazatriphosphinin-2-yl]oxy-benzoic acid) was synthesized and direct polycondensed with diphenylether or 1,4-diphenoxybenzene in Eaton's reagent at the temperature range of 80–120°C for 3 hours to give aromatic poly(ether ketone)s. Polycondensations at 120°C gave polymer of high molecular weight. Incorporation of cyclotriphosphazene groups in the aromatic poly(ether ketone) backbone greatly enhanced the solubility of these polymers in common organic polar solvents. Thermal stabilities by TGA for two polymer samples of polymer series ranged from 390 to 354°C in nitrogen at 10% weight loss and glass transition temperatures (T_g) ranged from 81.4 to 89.6°C by DSC. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1227–1232, 1998     

Syntheses and radical polymerization behavior of novel optically active methacrylamides having (L)-leucine structure in the side chains

Syntheses and radical polymerizations of methacrylamides having (L)-leucine and N-methyl-(L)-leucine methyl ester structures in the side chains N-methacryloyl-(L)-leucine methyl ester (MA-L-M) and N-methyl-N-methacryloyl-(L)-leucine methyl ester (N-Me-MA-L-M) were carried out. The monomers were prepared by the reactions of methacryloyl chloride with the corresponding amino acid methyl esters. Radical polymerizations were carried out in the presence of appropriate initiators at 60°C and 120°C. MA-L-M afforded the corresponding polymer with M_ns 38,000 ∼ 372,000 in high yields, while N-Me-MA-L-M afforded a trace amount of polymer at 60°C and in a low yield even at 120°C. Both inversion and increase of absolute value of specific rotation were observed in the transformation from MA-L-M (+1.3°C) to poly(MA-L-M) (−35.7°C). Changes in the CD spectral pattern and the conformation of the leucine moiety were confirmed from the monomer to polymer. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2681–2690, 1998     

Synthesis and thermal properties of thermosetting bis-benzocyclobutene–terminated arylene ether monomers

A series of new bis-benzocyclobutene-endcapped arylene ether monomers was prepared and characterized. Whereas 2,6-bis(4-benzocyclobutenyloxy)benzonitrile (BCB-EBN) could be prepared in good yield using the standard procedure (K₂CO₃/NMP/toluene/Dean–Stark trap/120°C), other bis(benzocyclobutene) (BCB)-terminated monomers containing ether-benzophenone (BCB-EK), ether-phenylsulfone (BCB-ES), and ether-6F-benzoxazole (BCB-EBO) moieties were invariably contaminated by mono-endcapped products under similar reaction conditions. This can be attributed to a much greater activating effect of the nitrile group on the ortho-fluorides in the aromatic nucleophilic displacement reaction than the carbonyl, sulfonyl, and benzoxazolyl groups. However, the latter monomers could be synthesized (70–80%) from 4-trimethylsiloxybenzocyclobutene and respective aromatic fluorides in the presence of CsF at 140°C. Similar curing behaviors under N₂ (DSC: extrapolated onset and peak temperatures at 227–230° and 260–262°C, respectively) characterized all four monomers. BCB-EK, BCB-ES, and BCB-EBN showed melting transitions at 108, 119, and 146°C, in that order. As BCB-EBO contained more rigid benzoxazole segments, it only exhibited a glass transition (T_g) at 85°C prior to curing exotherm, after it had been previously heated to 125°C. The following T_gs were observed for the cured materials: BCB-EK (201°C), BCB-EBN (224°C), BCB-ES (264°C), and BCB-EBO (282°C). The relative thermal stability according to TGA (He) results is: BCB-ES < BCB-EBN < BCB-EK < BCB-EBO. Finally, the results from thermal analysis, infrared spectroscopic, and variable temperature microscopic studies indicated that the nitrile group plays an important role in the cure chemistry, thermal, and microstructural properties of BCB-EBN. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2637–2651, 1998     

Cooperative motions in PVC studied by thermally stimulated currents: Comparison with A.C. dielectric derivative analysis

The thermally stimulated current–thermal sampling (TSC–TS) technique was used to study the broadened glass transition in conventional “atactic” poly(vinyl chloride), PVC. The activated parameters obtained from the TSC–TS data, mainly the apparent activation energy (E_a), characterize the breadth of glass transitions in a very sensitive way. These results are compared with those values of E_a obtained from the literature, using a recently proposed method of analyzing a.c. dielectric constants and their derivatives, over the temperature range of −100–130°C. Both techniques detect weak cooperative glass transition-like relaxations well below the main glass transition of ca. 80°C. As is the case with “atactic” PMMA, the data suggest that compositional heterogeneity related to a small fraction of predominantly isotactic sequences contribute to the broad glass transition extending ca. 60°C below the main glass transition in atactic PVC. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 913–918, 1998     

Thermal stability and nonisothermal crystallization of short fiber-reinforced poly(ether ether ketone) composites

The thermal stability of a short carbon-fiber-reinforced PEEK composite was assessed by thermogravimetry and by a Rheometrics dynamic analyzer. The results indicated that holding for 10 min at 380°C was a suitable melting condition to avoid the thermooxidative degradation under air. After proving that the heating rate of 50°C/min can be used to evaluate the crystallinity, a heating stage was used to prepare nonisothermally crystallized specimens using cooling rates from 1 to 100°C/min after melting at 400°C for 3 or 15 min. The degree of crystallinity and the melting behavior of these specimens were investigated by DSC at a heating rate of 50°C/min. The presence of three or four regions indicated that the upper melting temperature, T_m, changed with the crystallization temperature. The first region with the highest T_m, which corresponded to the cooling rate of 1°C/min, can be associated with the crystallization in regime II. There was a second region where T_m decreased as the amount of crystals formed in regime II decreased with increasing cooling rate from 5 to 20°C/min. The third region, a plateau region, corresponded to regime III condition in which the crystals were imperfect. In the fourth region, the cooling was so fast that crystallization was incomplete during the cooling for the melting condition of 400°C for 15 min. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2225–2235, 1998     

Application of zone-drawing and zone-annealing method to poly(p-phenylene sulfide) fibers

A zone-drawing and zone-annealing treatment was applied to poly(p-phenylene sulfide) fibers in order to improve their mechanical properties. The zone-drawing (ZD) was carried out at a drawing temperature of 90°C under an applied tension of 5.5 MPa, and the zone-annealing (ZA) was carried out at an annealing temperature of 220°C under 138.0 MPa. The differential scanning calorimetry (DSC) thermogram of the ZD fiber had a broad exothermic transition (T_c = 110°C) attributed to cold-crystallization and a melting endotherm peaking at 286°C. The T_c of the ZD fiber was lower than that (T_c = 128°C) of the undrawn fiber. In the temperature dependence of storage modulus (E′) for the ZD fiber, the E′ values decreased with increasing temperature, but increased slightly in the temperature range of 90–100°C, and decreased again. The slight increase in E′ was attributable to the additional increase in the crosslink density of the network, which was caused by strain-induced crystallization during measurement. The resulting ZA fiber had a draw ratio of 6.0, a degree of crystallinity of 38%, a tensile modulus of 8 GPa, and a tensile strength of 0.7 GPa. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1731–1738, 1998     

Ethylbenzene solubility,diffusivity, and permeability in poly(dimethylsiloxane)

The pure‐gas sorption, diffusion, and permeation properties of ethylbenzene in poly(dimethylsiloxane) (PDMS) are reported at 35, 45, and 55 °C and at pressures ranging from 0 to 4.4 cmHg. Additionally, mixed‐gas ethylbenzene/N₂ permeability properties at 35 °C, a total feed pressure of 10 atm, and a permeate pressure of 1 atm are reported. Ethylbenzene solubility increases with increasing penetrant relative pressure and can be described by the Flory–Rehner model with an interaction parameter of 0.24 ± 0.02. At a fixed relative pressure, ethylbenzene solubility decreases with increasing temperature, and the enthalpy of sorption is −41.4 ± 0.3 kJ/mol, which is independent of ethylbenzene concentration and essentially equal to the enthalpy of condensation of pure ethylbenzene. Ethylbenzene diffusion coefficients decrease with increasing concentration at 35 °C. The activation energy of ethylbenzene diffusion in PDMS at infinite dilution is 49 ± 6 kJ/mol. The ethylbenzene activation energies of permeation decrease from near 0 to −34 ± 7 kJ/mol as concentration increases, whereas the activation energy of permeation for pure N₂ is 8 ± 2 kJ/mol. At 35 °C, ethylbenzene and N₂ permeability coefficients determined from pure‐gas permeation experiments are similar to those obtained from mixed‐gas permeation experiments, and ethylbenzene/N₂ selectivity values as high as 800 were observed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1461–1473, 2000     

Covalent bonded polymer–graphene nanocomposites

This report describes a new route to covalently bonded polymer–graphene nanocomposites and the subsequent enhancement in thermal and mechanical properties of the resultant nanocomposites. At first, the graphite is oxidized by the modified Hummers method followed by functionalization with Octadecylamine (ODA). The ODA functionalized graphite oxides are reacted with methacryloyl chloride to incorporate polymerizable ? C?C? functionality at the nanographene platelet surfaces, which were subsequently employed in in situ polymerization of methylmethacrylate to obtain covalently bonded poly(methyl methacrylate) (PMMA)–graphene nanocomposites. The obtained nanocomposites show significant enhancement in thermal and mechanical properties compared with neat PMMA. Thus, even with 0.5 wt % graphene nanosheets, the T_g increased from 119 °C for neat PMMA to 131 °C for PMMA–graphene nanocomposite, and the respective storage modulus increased from 1.29 to 2 GPa. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4262–4267, 2010     

Copolymerization of ethyl α-(hydroxymethyl)acrylate with maleimide and characterization of the resulting copolymer

Copolymerization of maleimide (MI) and ethyl α-(hydroxymethyl)acrylate (EHMA) was performed at 60°C with AIBN as the initiator in THF. The monomer reactivity ratios were determined as r₁ (MI) = 0.13 and r₂ (EHMA) = 2.20. As the molar fraction of MI in the monomer feed increased, the initial rate of copolymerization decreased. TGA diagrams suggested the crosslinking reaction of the copolymer on heating. DSC and WAXD results suggested the existence of incomplete crystallinity in the copolymer. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1291–1299, 1998     

Effect of strain‐induced molecular ordering on mechanical performance and barrier properties of polylactide nanocomposites

Plastic deformation of polylactide has been known as a self‐reinforcement alternative to improve mechanical and barrier properties. In this study, the structural evolution was investigated during a hot‐drawing process, at different initial strain rates and temperatures above T_g of polylactide. The drawing process at T_g +10 °C, led to the formation of an intermediate molecular ordering, between the crystalline and amorphous phases. A lower fraction of this mesomorphic phase was found to develop with the addition of nanoparticles. An increase in the stretching temperature to T_g +30 °C, caused an improvement of the crystallization kinetics, compared to that of thermally activated crystallization. A strain hardening behavior was observed in the presence of mesophase during a stretching process of the hot‐drawn films at room temperature. Permeability was discerned to its basic components, diffusivity, and solubility coefficients. The matrix degradation influenced the permeability components. The diffusivity decreases in the presence of the impermeable matters. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1865–1876     

Thermally stable nonlinear optical polyurea functionalized by multiple charge‐transfer chromophore

A novel high glass‐transition temperature (272 °C) polyurea functionalized by a multiple charge‐transfer chromophore, 2‐{4‐[4,5‐bis(4‐nitrophenyl)imidazolyl]phenyl}‐4,5‐bis(4‐aminophenyl)imidazole, was synthesized. Simultaneous poling and polymerization and the in situ second‐harmonic generation (SHG) measurement technique was carried out to evaluate the thermal stability of the poling‐induced orientation. The nonlinear optical coefficient d₃₃ of poled polyurea film was 24 pm/V at 1064 nm fundamental wavelength. The SHG signal of the poled polymer film was quite stable below 200 °C and still remained 80% of its initial value after heating at 250 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4297–4301, 2002     

Evaluation of piezoelectric poly(vinylidene fluoride) polymers for use in space environments. I. Temperature limitations

Smart materials, such as thin‐film piezoelectric polymers, are interesting for potential applications on Gossamer spacecraft. This investigation aims to predict the performance and long‐term stability of the piezoelectric properties of poly(vinylidene fluoride) (PVDF) and its copolymers under conditions simulating the low‐Earth‐orbit environment. To examine the effects of temperature on the piezoelectric properties of PVDF, poly(vinylidenefluoride‐co‐trifluoroethylene), and poly(vinylidenefluoride‐co‐hexafluoropropylene), the d₃₃ piezoelectric coefficients were measured up to 160 °C, and the electric displacement/electric field (D–E) hysteresis loops were measured from ?80 to +110 °C. The room‐temperature d₃₃ coefficient of PVDF homopolymer films, annealed at 50, 80, and 125 °C, dropped rapidly within a few days of thermal exposure and then remained unchanged. In contrast, the TrFE copolymer exhibited greater thermal stability than the homopolymer, with d₃₃ remaining almost unchanged up to 125 °C. The HFP copolymer exhibited poor retention of d₃₃ at temperatures above 80 °C. In situ D–E loop measurements from ?80 to +110 °C showed that the remanent polarization of the TrFE copolymer was more stable than that of the PVDF homopolymer. D–E hysteresis loop and d₃₃ results were also compared with the deflection of the PVDF homopolymer and TrFE copolymer bimorphs tested over a wide temperature range. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1310‐1320, 2005     

Thermally induced polymerization of isobutylene in the presence of SnCl4: Kinetic study of the polymerization and NMR structural investigation of low molecular weight products

The polymerization reactivity of isobutylene/SnCl₄ mixtures in the absence of polar solvent, was investigated in a temperature interval from −78 to 60 °C. The mixture is nonreactive below −20 °C but slow polymerization proceeds from −20 to 20 °C with the initial rate r₀ of the order 10⁻⁵ mol · l⁻¹ · s⁻¹. The rate of the process increases with increasing temperature up to ∼10⁻² mol · l⁻¹ · s⁻¹ at 60 °C. Logarithmic plots of r₀ and M̄_n versus 1/T exhibit a break in the range from 20 to 35 °C. Activation energy is positive with values E = 21.7 ± 4.2 kJ/mol in the temperature interval from −20 to 35 °C and E = 159.5 ± 4.2 kJ/mol in the interval from 35 to 60 °C. The values of activation enthalpy difference of molecular weights in these temperature intervals are ΔH_Mn = −12.7 ± 4.2 kJ/mol and −38.3 ± 4.2 kJ/mol, respectively. The polymerization proceeds quantitatively, the molecular weights of products are relatively high, M̄_n = 1500–2500 at 35 °C and about 600 at 60 °C. It is assumed that initiation proceeds via [isobutylene · SnCl₄] charge transfer complex which is thermally excited and gives isobutylene radical‐cations. Oxygen inhibits the polymerization from −20 to 20 °C. Possible role of traces of water at temperatures above 20 °C is discussed. It was verified by NMR analysis that only low molecular weight polyisobutylenes are formed with high contents of exo‐ terminal unsaturated structures. In addition to standard unsaturated groups, new structures were detected in the products. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1568–1579, 2000     

Effects of Free Quenching on Mechanical,Thermomechanical and Thermophysical Properties of Titanium Dioxide-Pigmented Polystyrene

In this study, the effects of the free quenching temperature on mechanical, thermomechanical and thermophysical properties of pigmented polystyrene (PS/TiO₂) with 3% of TiO₂ were investigated. Thermal conductivity and thermal diffusivity of the titanium dioxide pigmented polystyrene were measured using a periodic method. The results show a slow improvement of the notched Izod impact strength obtained after a second quenching at 15 and 35°C; whereas thermal conductivity and diffusivity reached a minimum value at the quenching temperature of 35°C. However, the effect on the thermophysical properties is only noted for the second quenching temperature 35°C. The study allowed examining the effect of quenching temperature, filler concentration and material thickness on the transient thermal behavior of the titanium dioxide pigmented polystyrene.

     

Synthesis and rheology of biodegradable poly(glycolic acid) prepared by melt ring‐opening polymerization of glycolide

Ring‐opening polymerization (ROP) of glycolide was studied in melt conditions and in the presence of two different initiators: 1‐dodecanol and 1,4‐butanediol and tin(II) 2‐ethylhexanoate as catalyst. Its subsequent polymerization provided poly(glycolic acid) with controlled molar masses ranging from 2000 to 42,000 g/mol with well‐defined structures characterized by NMR. Their thermal properties were evaluated by DSC analysis, and a glass transition temperature at infinite molar mass (T_g∞) of 44.8 °C was thus calculated. From rheological data, the critical molar mass for entanglement, M_c, was estimated to be near 11,000 g/mol. Furthermore, in situ polymerizations were also performed between the plates of the rheometer within a same temperature range from 210 to 235 °C. The variation of the storage and loss moduli during the polymerization step have been monitored by time sweep oscillatory experiments under an angular frequency ω = 10 rad/s. Finally, the development of an inverse rheological method allowed to calculate the bulk polymerization kinetics in the temperature range 200–230 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1440–1449, 2009