Cyclic polypeptides by thermal polymerization of α‐amino acid N‐carboxyanhydrides

The NCAs of the following five amino acids were polymerized in bulk at 120 °C without addition of a catalyst or initiator: sarcosine (Sar), L ‐alanine (L ‐Ala), D ,L ‐phenylalanine (D ,L ‐Phe), D ,L ‐leucine (D ,L ‐Leu) and D ,L ‐valine (D,L ‐Val). The virgin reaction products were characterized by viscosity measurements ¹³C NMR spectroscopy and MALDI‐TOF mass spectrometry. In addition to numerous low molar mass byproducts cyclic polypeptides were formed as the main reaction products in the mass range above 800 Da. Two types of cyclic oligo‐ and polypeptides were detected in all cases with exception of sarcosine NCA, which only yielded one class of cyclic polypeptides. The efficient formation of cyclic oligo‐ and polypeptides explains why high molar mass polymers cannot be obtained by thermal polymerizations of α‐amino acid NCAs. Various polymerization mechanisms were discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4012–4020, 2008     

Cationic polymerizations of 2‐alkyloxazolines catalyzed by bismuth salts

Acidic bismuth salts, such as BiCl₃, BiBr₃, BiJ₃, and Bi‐triflate catalyzed the ring‐opening polymerization of 2‐methoxazoline (MOZ) in bulk at 100 °C, whereas less acidic salts such as Bi₂O₃ or Bi(III)acetate did not. Bi‐triflate‐catalyzed polymerizations of 2‐ethyloxazoline (EtOZ) were performed with variation of the monomer–catalyst ratio (M/C). It was found that the molecular weights were independent of the M/C ratio. The formation of cationic chain ends and the absence of cycles was proven by reactions of virgin polymerization products with N,N‐dimethyl‐4‐aminopyridine or triphenylphosphine. The resulting polymers having modified cationic chain ends were characterized by ¹H NMR spectroscopy and MALDI‐TOF mass spectrometry. The polymerization mechanism including chain‐transfer reactions is discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4777–4784, 2008     

Syntheses of multicyclic poly(ether sulfone)s from 5,5′,6,6′‐tetrahydroxy‐3,3,3′,3′‐tetramethyl spirobisindane and 4,4′‐bis(4‐chlorophenyl) sulfones

5,5′,6,6′‐Tetrahydroxy‐3,3,3′,3′‐tetramethyl spirobisindane (TTSBI) was polycondensed with 4,4′‐dichlorodiphenyl sulfone (DCDPS) or with 4,4′‐bis(4‐chlorophenyl sulfonyl) biphenyl (BCSBP) in DMSO. Concentration and feed ratio were optimized to avoid gelation and to obtain a maximum yield of multicyclic polyethers free of functional groups. Regardless of these reaction conditions, only low fractions of perfect multicycles were obtained from DCDPS apparently due to steric hindrance of ring closure. Under the same conditions high fractions of perfect multicycles were achieved with the longer and more flexible DCSBP. The reaction products were characterized by MALDI‐TOF mass spectrometry, ¹H‐NMR spectroscopy viscosity, and DSC measurements. Relatively low glass transition temperatures (T_gs ≈ 160–175 °C) were found. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3732–3739, 2008     

Kinetic study of copper(I)‐catalyzed click chemistry step‐growth polymerization

Oligomers and polymers containing triazole units were synthesized by the copper(I)‐catalyzed 1,3‐dipolar cycloaddition step‐growth polymerization of four difunctional azides and alkynes. In a first part, monofunctional benzyl azide was used as a chain terminator for the polyaddition of 1,6‐diazidohexane and α,ω‐bis(O‐propargyl)diethylene glycol, leading to polytriazole oligomers of controlled average degree of polymerization (DP_n = 3–20), to perform kinetic studies on low‐viscosity compounds. The monitoring of the step‐growth click polymerization by ¹H NMR at 25, 45, and 60 °C allowed the determination of the activation energy of this click chemistry promoted polyaddition process, that is, E_a = 45 ± 5 kJ/mol. The influence of the catalyst content (0.1–5 mol % of Cu(PPh₃)₃Br according to azide or alkyne functionalities) was also examined for polymerization kinetics performed at 60 °C. In a second part, four high molar mass polytriazoles were synthesized from stoichiometric combinations of diazide and dialkyne monomers above with p‐xylylene diazide and α,ω‐bis(O‐propargyl)bisphenol A. The resulting polymers were characterized by DSC, TGA, SEC, and ¹H NMR. Solubility and thermal properties of the resulting polytriazoles were discussed based on the monomers chemical structure and thermal analyses. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5506–5517, 2008     

Bismuth halide‐catalyzed polymerizations of ε‐caprolactone

In contrast to BiF₃, the other three Bi‐halides catalyzed the ring‐opening polymerization of ε‐caprolactone (ε‐CL) in bulk. A temperature of 140 °C was found to be advantageous for rapid polymerization and optimum molecular weights. At this temperature, the reactivity of the catalysts increases in the order BiCl₃ < BiBr₃ < BiJ₃. Variation of the monomer‐catalyst ratio (M/C) yielded number‐average molecular weights (M_ns) up to 80,000 Da (corrected SEC data, 120,000 Da uncorrected), but a proper control of the M_ns was not achieved. In addition to CH₂? OH endgroups, CH₂Cl, CH₂Br, and CH₂J endgroups were detected, but no evidence for a cationic polymerization mechanism was found. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7483–7490, 2008     

Synthesis of low‐polydispersity poly(N‐ethylmethylacrylamide) by controlled radical polymerizations and their thermal phase transition behavior

Controlled radical polymerizations of N‐ethylmethylacrylamide (EMA) by atom transfer radical polymerization and reversible addition‐fragmentation chain transfer processes were investigated in detail for the first time, employing complementary characterization techniques including gel permeation chromatography, ¹H NMR spectroscopy, and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry. In both cases, relatively good control of the polymerization of EMA was achieved, as revealed by the linear evolution of molecular weights with monomer conversions and the low polydispersity of poly(N‐ethylmethylacrylamide) (PEMA). The thermal phase transitions of well‐defined PEMA homopolymers with polydispersities less than 1.2 and degrees of polymerization up to 320 in aqueous solution were determined by temperature‐dependent turbidity measurements. The obtained cloud points (CPs) vary in the range of 58–68 °C, exhibiting inverse molecular weight and polymer concentration dependences. Moreover, the presence of a carboxyl group instead of an alkyl one at the PEMA chain end can elevate its CP by ～3–4 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 60–69, 2008     

Homogeneous tandem catalysis of the bis‐(diphenylphosphino)‐amine/chromium tetramerization catalyst with metallocene catalysts

Homogeneous tandem catalysis of the bis(diphenylphoshino)amine‐chromium oligomerization catalyst with the metallocenes Ph₂C(Cp)(9‐Flu)ZrCl₂ and rac‐EtIn₂ZrCl₂, is discussed. GC, CRYSTAF, and ¹³C NMR analysis of the products obtained from reactions at constant temperatures show that during tandem catalysis, α‐olefins, mainly 1‐hexene and 1‐octene, are produced from ethylene by the oligomerization catalyst and subsequently built into the polyethylene chain. At 40 °C the Cr/PNP catalyst acts as a tetramerization catalyst while the polymerization catalyst activity is low. Copolymerization of ethylene and the in situ produced α‐olefins have also been carried out by increasing the temperature from 40 °C, where primarily oligomerization takes place, to above 100 °C, where polymerization becomes dominant. The melting temperature of the polymer is dependent on the catalyst and cocatalyst ratios as well as on the temperature gradient followed during the reaction, while the presence of the oligomerization catalyst reduces the activity of the polymerization catalyst. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6847–6856, 2006     

Polymerization of methyl methacrylate by 2‐pyrrolidinone and n‐dodecyl mercaptan

The bulk polymerization of methyl methacrylate initiated with 2‐pyrrolidinone and n‐dodecyl mercaptan (R‐SH) has been explored. This polymerization system showed “living” characteristics; for example, the molecular weight of the resulting polymers increased with reaction time by gel permeation chromatographic analysis. Also, the polymer was characterized by Fourier transform infrared spectroscopy, ¹H NMR, and ¹³C NMR techniques. The polymer end with the iniferter structures was found. By the initial‐rate method, the polymerization rate depended on [2‐pyrrolidinone]^1.0 and [R‐SH]⁰. Combining the structure analysis and the polymerization‐rate expression, a possible mechanism was proposed. n‐Dodecyl mercaptan served dual roles—as a catalyst at low conversion and as a chain‐transfer agent at high conversion. Finally, the thermal properties were studied, and the glass‐transition temperature and thermal‐degradation temperature were, respectively, 25 and 80–100 °C higher than that of the azobisisobutyronitrile system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3692–3702, 2002     

High‐quality poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] synthesized by a solid–liquid two‐phase reaction: Characterizations and electroluminescence properties

Poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] (MEH‐PPV) with a molar mass of 26–47 × 10⁴ g mol^?1 and a polydispersity of 2.5–3.2 was synthesized by a liquid–solid two‐phase reaction. The liquid phase was tetrahydrofuran (THF) containing 1,4‐bis(chloromethyl)‐2‐methoxy‐5‐(2′‐ethylhexyloxy)benzene as the monomer and a certain amount of tetrabutylammonium bromide as a phase‐transfer catalyst. The solid phase consisted of potassium hydroxide particles with diameters smaller than 0.5 mm. The reaction was carried out at a low temperature of 0 °C and under nitrogen protection. No gelation was observed during the polymerization process, and the polymer was soluble in the usual organic solvents, such as chloroform, toluene, THF, and xylene. A polymer light‐emitting diode was fabricated with MEH‐PPV as an active luminescent layer. The device had an indium tin oxide/poly(3,4‐ethylenedioxylthiophene) (PEDOT)/MEH‐PPV/Ba/Al configuration. It showed a turn‐on voltage of 3.3 V, a luminescence intensity at 6.1 V of 550 cd/m², a luminescence efficiency of 0.43 cd/A, and a quantum efficiency of 0.57%. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3049–3054, 2004     

Kinetics of hexene‐1 polymerization using [(N,N′‐diisopropylbenzene)‐2,3‐(1,8‐napthyl)‐1,4‐diazabutadiene] dibromonickel/methylaluminoxane catalyst system

Kinetics of hexene‐1 polymerization was investigated using [(N,N′‐diisopropylbenzene)2,3‐(1,8‐napthly)‐1,4‐diazabutadiene]dibromonickel/methylaluminoxane catalyst. Experiments were performed at varying catalyst and monomer concentrations in the temperature range of ?10 to 35 °C. First order time‐conversion plot shows a downward curvature at temperatures of 20 °C and 35 °C indicating the presence of finite termination reactions. A nonlinear plot of degree of polymerization (P_n) with respect to conversion indicates occurrence of transfer reactions and slow initiation. The experimental molar masses are higher than predicted, which implies that a fraction of catalyst species could not be activated or is deactivated at the early stages of the reactions. The efficiency of the catalyst (Cat_eff) varies from 0.77 to 0.89. The observed polydispersity of the poly(hexene‐1) s is in the range of 1.18–1.48. The reaction order was found to be 1.11 with respect to catalyst. The Arrhenius plot obtained using the overall propagation rate constant, k_p, at five different temperatures (?10, 0, 10, 20, and 35 °C) was found to be linear with an activation energy, E_a = 4.3 kcal/mol. Based on the results presented it is concluded that the polymerization of hexene‐1 under the above‐mentioned conditions shows significant deviation from ideal “living” behavior. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1093–1100, 2007     

Physical characterization of poly(ω‐pentadecalactone) synthesized by lipase‐catalyzed ring‐opening polymerization

The Candida antarctica lipase B (Novozyme‐435)‐catalyzed ring‐opening polymerization of ω‐pentadecalactone in toluene was performed. Poly(ω‐pentadecalactone) [poly(PDL)] was obtained in a 93% isolated yield in 4 h with a number‐average molecular weight of 64.5 × 10³ g/mol and a polydispersity index of 2.0. The solid‐state properties of poly(PDL) were investigated by thermogravimetric analysis (TGA) coupled with mass spectrometry, differential scanning calorimetry (DSC), stress–strain measurements, wide‐angle X‐ray diffraction, and dynamic mechanical and dielectric spectroscopies. Poly(PDL) is a crystalline polymer that melts around 100 °C. The polyester shows good thermal stability, with a main TGA weight loss centered at 425 °C. Because of the high degree of poly(PDL) crystallinity, the glass transition (?27 °C) is revealed by relaxation techniques such as dynamic mechanical and dielectric spectroscopies, rather than by DSC. In addition to the glass transition, the viscoelastic spectrum of poly(PDL) also shows two low‐temperature secondary relaxations centered at ?130 (γ) and ?90 °C (β). They are attributed to local motions of the long methylene sequence (γ) and complex units involving water associated with the ester groups (β). The mechanical properties of poly(PDL) are typical of a hard, tough material, with an elastic modulus and yield parameters comparable to those of low‐density polyethylene. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1721–1729, 2001     

Ring‐opening polymerization of L‐lactide by rare‐earth tris(4‐tert‐butylphenolate) single‐component initiators

The ring‐opening polymerization of L ‐lactide initiated by single‐component rare‐earth tris(4‐tert‐butylphenolate)s was conducted. The influences of the rare‐earth elements, solvents, temperature, monomer and initiator concentrations, and reaction time on the polymerization were investigated in detail. No racemization was found from 70 to 100 °C under the examined conditions. NMR and differential scanning calorimetry measurements further confirmed that the polymerization occurred without epimerization of the monomer or polymer. A kinetic study indicated that the polymerization rate was first‐order with respect to the monomer and initiator concentrations. The overall activation energy of the ring‐opening polymerization was 79.2 kJ mol^?1. ¹H NMR data showed that the L ‐lactide monomer inserted into the growing chains with acyl–oxygen bond cleavage. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6209–6215, 2004     

Low‐temperature controlled free‐radical polymerization of vinyl monomers in the presence of a novel cyclic dixanthate under γ‐ray irradiation

The free‐radical polymerization of methyl acrylate (MA) has been studied in the presence of a novel cyclic dixanthate under γ‐ray irradiation (80 Gy min^?1) at room temperature (～28 °C), ?30 °C, and ?76 °C respectively. The resultant polymers have controlled molecular weights and relatively narrow molecular weight distributions, especially at low temperatures (i.e., ?30 and ?76 °C). The polymerization control may be associated with the temperature: the lower the temperature is, the more control there is. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis of poly(methyl acrylate) (PMA) samples shows that there are at least three distributions: [3‐(MA)_n‐H]⁺ cyclic polymers, [3‐(MA)_n‐THF‐H]⁺, and [3‐(MA)_n‐(THF)₂‐H]⁺ linear PMAs. The relative content of the cyclic polymers markedly increases at a lower temperature, and this may be related to the reduced diffusion rate and the suppressed chain‐transfer reaction at the low temperature. It is evidenced that the good control of the polymerization at the low temperature may be associated with the suppressed chain‐transfer reaction, unlike reversible addition–fragmentation chain transfer polymerization. In addition, styrene bulk polymerizations have been performed, and gel permeation chromatography traces show that there is only one cyclic dixanthate moiety in the polymer chain. This article is the first to report the influence of a low temperature on controlled free‐radical polymerizations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2847–2854, 2007     

Microwave‐assisted ring‐opening polymerization of ϵ‐caprolactone

Ring‐opening polymerization of ?‐caprolactone was carried out smoothly and effectively with constant microwave powers of 170, 340, 510, and 680 W, respectively, with a microwave oven at a frequency of 2.45 GHz. The temperature of the polymerization ranged from 80 to 210 °C. Poly(?‐caprolactone) (PCL) with a weight‐average molar mass (M_w) of 124,000 g/mol and yield of 90% was obtained at 680 W for 30 min using 0.1% (mol/mol) stannous octanoate as a catalyst. When the polymerization was catalyzed by 1% (w/w) zinc powder, the M_w of PCL was 92,300 g/mol after the reaction mixture was irradiated at 680 W for 270 min. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1749–1755, 2002     

Ring opening polymerization and copolymerization of L‐lactide and ɛ‐caprolactone by bis‐ligated magnesium complexes

Seven magnesium complexes ( 1–7 ) were synthesized by reaction of new ( L ³ ‐H – L ⁵ ‐H ) and previously reported ketoimine pro‐ligands with dibutyl magnesium and were isolated in 59–70% yields. Complexes 1–7 were characterized fully and consisted of bis‐ligated homoleptic ketoiminates coordinated in distorted octahedral geometry around the magnesium centers. The complexes were investigated for their ability to initiate the ring opening polymerization (ROP) of l ‐lactide (L‐LA) to poly‐lactic acid (PLA) and ?‐caprolactone (?CL) to poly‐caprolactone in the presence of 4‐fluorophenol co‐catalyst. For L‐LA polymerization, complexes containing ligand electron‐donating groups ( 1–5 ) achieved >90% conversion in 2 h at 100 °C, while the presence of CF₃ groups in 6 and 7 slowed or resulted in no PLA detected. With ?CL, ROP initiated with 1–7 resulted in lower percentage conversion with similar electronic effects. Moderate molecular weight PLA polymeric material (14.3–21.3 kDa) with low polydispersity index values (1.23–1.56) was obtained, and ROP appeared to be living in nature. Copolymerization of L‐LA and ?CL yielded block copolymers only from the sequential polymerization of ?CL followed by L‐LA and not the reverse sequence of monomers or the simultaneous presence of both monomers. Polymers and copolymers were characterized with NMR, gel permeation chromatography, and differential scanning calorimetry. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 48–59     

Synthesis of novel hyperbranched poly(ester‐amide)s based on neutral α‐amino acids via “AD + CBB′” couple‐monomer approach

A series of novel hyperbranched poly(ester‐amide)s (HBPEAs) based on neutral α‐amino acids have been synthesized via the “AD + CBB′” couple‐monomer approach. The ABB′ intermediates were stoichiometrically formed through thio‐Michael addition reaction because of reactivity differences between functional groups. Without any purification, in situ self‐polycondensations of the intermediates at elevated temperature in the presence of a catalyst afforded HBPEAs with multihydroxyl end groups. The degrees of branching (DBs) of the HBPEAs were estimated to be 0.40–0.58 and 0.24–0.54 by quantitative ¹³C NMR with two different calculation methods, respectively, depending on polymerization conditions and structure of monomers. The influences of catalyst, temperature, and intermediate structure on the polymerization process and molecular weights as well as properties of the resultant polymers were investigated. FTIR, NMR, and DEPT‐135 NMR analyses revealed the branched structure of the resultant polymers. The HBPEAs possess moderately high molecular weights with broad distributions, glass transition temperatures in the range of ?25.5 to 36.5 °C, and decomposition temperatures at 10% weight loss under nitrogen and air in the regions of 243.4–289.1 °C and 231.4–265.6 °C, respectively. Among them, those derived from D ,L ‐phenylalanine display the lowest degree of branching, whereas the highest glass transition temperature and the best thermal stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Coupling selectivity in the radical‐controlled oxidative polymerization of 4‐phenoxyphenol catalyzed by (1,4,7‐triisopropyl‐1,4,7‐triazacyclononane)copper(II) complex

Various effects on the coupling selectivity of the oxidative polymerization of 4‐phenoxyphenol catalyzed by (1,4,7‐triisopropyl‐1,4,7‐triazacyclononane)copper(II) halogeno complex [Cu(tacn)X₂] are described. With respect to the amount of the catalyst and the nature of the halide ion (X) of Cu(tacn)X₂, the coupling selectivity hardly changed. The Cu(tacn) catalyst possessed a turnover number greater than 1860. As the temperature of the reaction and the polarity of the reaction solvent were elevated, the C O coupling at the o‐position increased, but the C C coupling was not involved. For the polymerization in toluene at 80 °C, poly(1,4‐phenylene oxide), obtained as a methanol‐insoluble part, showed the highest number‐average molecular weight of 4000 with a melting point (T_m) of 195 °C. Only a slight change in the coupling selectivity was observed in the presence or absence of hindered amines as the base. Surprisingly, however, the C O selectivity decreased from 100 to 24% with less hindered amines, indicating that the selectivity drastically changed from a preference for C O coupling to a preference for C C coupling. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4792–4804, 2000     

Cationic addition polymerization of 1,4‐dioxene using gacl3 as lewis acid catalyst: Long‐lived species‐mediated polymerization

Effective cationic addition polymerization of 1,4‐dioxene, a six‐membered cyclic olefin with two oxygen atoms adjacent to the double bond, was performed using a simple metal halide catalyst system in dichloromethane. The polymerization was controlled when the reaction was conducted using GaCl₃ in conjunction with an isobutyl vinyl ether–HCl adduct as a cationogen at –78°C to give polymers with predetermined molecular weights and relatively narrow molecular weight distributions. The long‐lived properties of the propagating species were further confirmed by a monomer addition experiment and the analyses of the product polymers by ¹H NMR and MALDI–TOF–MS. Although highly clean propagation proceeded, the apparent rate constant changed during the controlled cationic polymerization of 1,4‐dioxene. The reason for the change was discussed based on polymerization results under various conditions. The obtained poly(1,4‐dioxene) exhibited a very high glass transition temperature (T_g) of 217°C and unique solubility. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Microwave‐assisted ring‐opening polymerization of p‐dioxanone

The ring‐opening polymerization (ROP) of p‐dioxanone (PDO) under microwave irradiation with triethylaluminum (AlEt₃) or tin powder as catalyst was investigated. When the ROP of PDO was catalyzed by AlEt₃, the viscosity‐average molecular weight (M_v) of poly(p‐dioxanone) (PPDO) reached 317,000 g mol^?1 only in 30 min, and the yield of PPDO achieved 96.0% at 80 °C. Tin powder was successfully used as catalyst for synthesizing PPDO by microwave heating, and PPDO with M_v of 106,000 g mol^?1 was obtained at 100 °C in 210 min. Microwave heating accelerated the ROP of PDO catalyzed by AlEt₃ or tin powder, compared with the conventional heating method. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3207–3213, 2008     

Solid‐state amidization and imidization reactions in vapor‐deposited poly(amic acid)

The condensation polymerization of 4,4′‐oxydianiline with pyromellitic dianhydride for the formation of poly(amic acid) and the subsequent imidization for the formation of polyimides were investigated for films prepared with vapor‐deposition polymerization techniques. Fourier transform infrared spectroscopy, thermal analysis, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry of films at different temperatures indicated that additional solid‐state polymerization occurred before imidization. The experiments revealed that, upon vapor deposition, poly(amic acid) oligomers formed that had a number‐average molecular weight of about 1500 Da. Between 100–130 °C, these chains underwent an additional condensation reaction and formed slightly higher molecular weight oligomers. Calorimetry measurements showed that this reaction was exothermic [enthalpy of reaction (ΔH) ～ ?30 J/g] and had an activation energy of about 120 kJ/mol. The experimental ΔH values were compared with results from ab initio molecular modeling calculations to estimate the number of amide groups formed. At higher temperatures (150–300 °C), the imidization of amide linkages occurred as an endothermic reaction (ΔH ～ +120 J/g) with an activation energy of about 130 kJ/mol. The solid‐state kinetics depended on the reaction conversion as well as the processing conditions used to deposit the films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5999–6010, 2004