Copolymerization of N‐substituted maleimide with alkyl acrylate and its industrial applications

A series of new copolymers with desired thermal stability and mechanical properties for applications in leather industry were synthesized from various substituted maleimides and alkyl acrylates. Polymerization was carried out by a free‐radical polymerization using benzoyl peroxide (BPO) as initiator. The monomers and polymers synthesized were characterized by elemental analysis, IR, and nuclear magnetic resonance (NMR). Interestingly, these polymers were soluble in common organic solvents. Copolymer composition and reactivity ratios were determined by ¹H‐NMR spectra. The molecular weights of the polymers were determined by gel permeation chromatography. The homo‐ and copolymer of maleimide showed single‐stage decomposition (ranging from 300–580°C). The initial decomposition temperatures of poly[N‐(phenyl)maleimide] [poly(PM)], poly[N‐4‐(methylphenyl)maleimide] [poly(MPM)] and poly[N‐3‐(chlorophenyl)maleimide] [poly(CPM)] were higher compared to those of the copolymers. Heat‐resistant adhesives such as blends of epoxy resin with phenyl‐substituted maleimide‐co‐glycidyl methacrylate copolymers with improved adhesion property were developed. Different adhesive formulations of these copolymaleimides were prepared by curing with diethanolamine at two different temperatures (30°C and 60°C). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1870–1879, 2001     

Thermal analysis and mechanical characterization of maleimide‐functionalized benzoxazine/epoxy copolymers

Maleimide‐functionalized benzoxazine is copolymerized with epoxy to improve toughness and processibility without compromising the thermal properties. The incorporation of maleimide functionality into the benzoxazine monomer results in a high performance polymer. All three possible polymerization reactions are confirmed using Fourier transform infrared (FT‐IR) spectroscopy. While maleimide‐functionalized benzoxazine has a glass transition temperature, T_g, of 252°C, a further 25°C increase of T_g is observed when copolymerized with epoxy. The flexural properties are also measured, and the copolymers exhibit a flexural modulus of 4.2–5.0 GPa. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1670–1677, 2006     

Synthesis and chain extension of nitroxide‐terminated styrene–maleimide copolymers

Thermal radical copolymerization of styrene (S) and maleimide (MI) at 125°C in diglyme in the presence of 2,2,6,6‐tetramethylpiperidin‐1‐yloxyl radical (TEMPO) was studied. Mole fractions of maleimide in the feed, F_MI, varied in the range 0.1–0.9. A quasiliving reaction process proceeded yielding copolymers with a low polydispersity (M_w/M_n = 1.17–1.41). The found azeotropic composition, (F_MI)_A = 0.46, did not differ substantially from that (0.5) in the conventional radical S‐MI copolymerization. At a higher conversion or MI content in the feed, deactivation of the copolymer chains occurred. The obtained TEMPO‐terminated S‐MI copolymers readily initiated polymerization of styrene; chain extension of the macroinitiators took place, giving poly(S‐co‐MI)‐block‐poly(S) diblock copolymers. The synthesized copolymers containing S and MI units were characterized by elemental analysis, NMR spectroscopy, size‐exclusion chromatography, and differential scanning calorimetry. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1863–1868, 2004     

Nitroxide‐terminated poly(styrene‐co‐diethyl fumarates) and derived block copolymers

Copolymerization of styrene (S) and diethyl fumarate (DEF) at 125°C in the presence of 2,2,6,6‐ tetramethylpiperidin‐1‐yloxyl radical (TEMPO) and initiated with a thermal initiator, 2,2′‐azobisisobutyronitrile (AIBN), was studied. The molar fraction of DEF in the feed, F_DEF, varied within 0.1–0.9. An azeotropic composition, (F_DEF)_A = 0.38, was found for the copolymerization under study. At F_DEF = 0.1–0.4, a quasi‐living process was observed, transforming to a retarded conventional radical copolymerization at a higher content of DEF in the initial mixtures. The obtained TEMPO‐terminated S‐DEF copolymers were used to initiate polymerization of styrene. Poly(styrene‐ co‐diethyl fumarate)‐block‐polystyrene copolymers were prepared with molecular weight distributions depending on the amount of inactive polymer chains in macroinitiators, as indicated by size‐exclusion chromatography. A limited miscibility of the blocks in the synthesized block copolymers was revealed by using differential scanning calorimetry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2432–2439, 2002     

Crystallization kinetics of poly(1,4‐butylene‐co‐ethylene terephthalate)

The crystallization kinetics of poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET), and their copolymers poly(1,4‐butylene‐co‐ethylene terephthalate) (PBET) containing 70/30, 65/35 and 60/40 molar ratios of 1,4‐butanediol/ethylene glycol were investigated using differential scanning calorimetry (DSC) at crystallization temperatures (T_c) which were 35–90 °C below equilibrium melting temperature . Although these copolymers contain both monomers in high proportion, DSC data revealed for copolymer crystallization behaviour. The reason for such copolymers being able to crystallize could be due to the similar chemical structures of 1,4‐butanediol and ethylene glycol. DSC results for isothermal crystallization revealed that random copolymers had a lower degree of crystallinity and lower crystallite growth rate than those of homopolymers. DSC heating scans, after completion of isothermal crystallization, showed triple melting endotherms for all these polyesters, similar to those of other polymers as reported in the literature. The crystallization isotherms followed the Avrami equation with an exponent n of 2–2.5 for PET and 2.5–3.0 for PBT and PBETs. Analyses of the Lauritzen–Hoffman equation for DSC isothermal crystallization data revealed that PBT and PET had higher growth rate constant G_o, and nucleation constant K_g than those of PBET copolymers. © 2001 Society of Chemical Industry     

Microstructure analysis of N‐vinyl‐2‐pyrrolidone/vinyl acetate copolymers by NMR spectroscopy

N‐Vinyl‐2‐pyrrolidone (V) and vinyl acetate (A) copolymers of different compositions were synthesized by free radical bulk polymerization. The copolymer composition of these copolymers was determined using quantitative ¹³C{¹H} NMR spectra. The reactivity ratios for these comonomers were determined using the Kelen–Tudos (KT) and non‐linear least‐square error‐in‐variable (EVM) methods. The reactivity ratios calculated from the KT and EVM methods are r_V = 2.86 ± 0.16, r_A = 0.36 ± 0.09 and r_V = 2.56, r_A = 0.33, respectively. ¹H, ¹³C{¹H} and ¹H–¹³C heteronuclear shift correlation spectroscopy (HSQC) and ¹H–¹H homonuclear total correlation spectroscopy (TOCSY) were used for the compositional and configurational assignments of V/A copolymers. The ¹³C distortionless enhancement by polarization transfer (DEPT) technique was used to resolve the methine, methylene and methyl resonance signals in the V/A copolymers. © 2002 Society of Chemical Industry     

Design,synthesis, and photosensitive performance of polymethacrylate‐positive photoresist‐bearing o‐nitrobenzyl group

Novel polymethacrylate‐positive photoresist‐bearing o‐nitrobenzyl group was described herein. The matrix polymer (PCHIBNB) was synthesized by copolymerization of cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBMA), and o‐nitrobenzyl methacrylate (NBMA) via reversible addition fragmentation chain transfer (RAFT) polymerization method. After UV irradiation, the o‐nitrobenzyl groups of PCHIBNB were photocleaved and the resulting carboxyl groups were highly alkali‐soluble, so that the matrix polymer could be etched by mild alkali solution with no requirements of photosensitizers or photoacid generators. PCHIBNB was characterized by Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H‐NMR) spectroscopy, and gel permeation chromatography (GPC). The photocleavable behaviors of PCHIBNB were determined by FTIR, ¹H‐NMR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) analysis. The resist formulated with this polymer and cast in tetrahydrofuran (THF) solution showed 10 μm × 10 μm square pattern using a mercury–xenon lamp in a contact printing mode and tetramethyl‐ammonium hydroxide aqueous solution as a developer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41733.     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Synthesis and characterization of optically active star‐shaped poly (N‐phenylmaleimide)s with a calixarene core

Two N‐phenylmaleimide derivatives bearing a chiral oxazoline group, N‐[o‐(4‐phenyl‐4,5‐dihydro‐1,3‐oxazol‐2‐yl)phenyl]maleimide [(R)‐PhOPMI] and N‐[o‐(4‐isopropyl‐4,5‐dihydro‐1,3‐oxazol‐2‐yl)phenyl]maleimide [(S)‐PrⁱOPMI], were polymerized using in situ generated calixarene‐based phenates as initiators to yield optically active polymers. The formation of star‐shaped architectures was strongly dependent on both polymerization conditions and calixarene moieties. In the case of polymerization conducted in toluene at 80–100 °C, the arm‐chain numbers achieved their respective maxima for the polymers with these multifunctional initiators. In contrast, the polymers obtained in polymerizations at lower temperature possessed fewer arm chains. The structure and chiroptical properties were investigated on the basis of ¹³C NMR, multiangular laser light scattering, gel permeation chromatography, and circular dichroism for the macromolecules with calixarene cores. Copyright © 2006 Society of Chemical Industry     

Synthesis and characterization of anionic graft copolymers containing poly(ethylene oxide) grafts

Graft copolymers containing poly(ethylene oxide) side chain attached to maleic anhydride‐alt‐vinyl methyl ether (MA‐VME) copolymer were prepared by coupling MA‐VME and poly(ethylene glycol) monomethyl ether (MPEG) by esterification in DMF at 90°C. MPEG and dodecyl alcohol (DA) were grafted onto MA‐VME copolymer in o‐xylene at 140°C in the presence of p‐toluene sulfonic acid as catalyst. The molecular weights of MPEG were found to influence the rate of the grafting reaction and the final degree of conversion. The graft copolymers were characterized by IR, GPC, and ¹H‐NMR. DSC was used to examine thermal properties of the graft copolymers. The analysis indicates that grafts have phase‐separated morphology with the backbone and the MPEG grafts forming separate phases. The properties in aqueous solutions of these grafts were studied with respect to aggregation behavior and viscometric properties. In aqueous solution, the polymers exhibited polyelectrolyte behavior (i.e., a dramatic increase of the viscosity upon neutralization). Graft copolymers with DA have lower viscosities. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1138–1148, 2002     

Synthesis and electrical properties of copolymers of o‐phenylenediamine with aniline, 3,4‐ethylenedioxythiophene and 2,3,5,6‐tetrafluoroaniline

Copolymers (P(PDA/Ar)) of o‐phenylenediamine with aniline (Ar = ANi), 3,4‐ethylenedioxythiophene (Ar = EDOT) and 2,3,5,6‐tetrafluoroaniline (Ar = TFANi) were synthesized via polycondensation initiated by ammonium persulfate. The NH₂ group content in the copolymers was determined by analyzing the ¹H NMR spectra of the N‐acetylated copolymers. Copolymers crosslinked by viologen (1,1'‐disubstituted 4,4'‐bipyridinium dichloride) were obtained by reaction involving the reactive NH₂ groups in the copolymers. The absorption wavelengths of solutions of the copolymers and the electrochemical oxidation and reduction potentials of cast films of the copolymers were affected by the electrical properties of the Ar unit. © 2016 Society of Chemical Industry     

Synthesis and characterization of degradable copoly(ester–amide)s: Poly(trans‐4‐hydroxy‐L‐proline‐co‐ε‐caprolactam)

Novel copolyesteramides were synthesized by reacting trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) with ε‐caprolactam (CLM) in the presence of stannous octoate [Sn(II) Oct.] as a catalyst. Various techniques, including ¹H‐NMR, IR, DSC, and viscosity, were used to elucidate structural characteristics and thermal properties of the resulting copolymers. Data showed that the optimal reaction condition for the synthesis of the copolymers was obtained by using 3 wt % Sn(II) Oct. at 170°C for 24 h. The DSC analysis demonstrated amorphous structure for most of the copolymers. The glass‐transition temperature of the copolymers shifts to a higher temperature with increasing Hpr/CLM molar ratio. In vitro degradation of these poly(N‐CBz‐Hpr‐co‐CLM)s was evaluated by weight loss measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1615–1621, 2002     

Synthesis of oligo‐ortho‐azomethinephenol and its oligomer–metal complexes: Characterization and application as anti‐microbial agents

The oxidative polycondensation reaction conditions and optimum parameters of o‐phenylazomethinephenol (PAP) with oxygen (air) and NaOCl were determined in an aqueous alkaline solution at 60–98°C. The properties of oligo‐o‐phenylazomethinephenol (OPAP) were studied by chemical and spectra analyses. PAP was converted to dimers and trimers (25–60%) by oxidation in an aqueous alkaline medium. The number average molecular weight (M_n), mass average molecular weight (M_w), and polydispersity index (PDI) values were 1180 g mol^?1, 1930 g mol^?1, and 1.64, respectively. According to these values, 20–33% of PAP turned into OPAP. During the polycondensation reaction, a part of the azomethine (? CH?N? ) groups oxidized to carboxylic (? COOH) group. Thus, a water‐soluble fraction of OPAP was incorporated in the carboxylic (? COOH); (2–20%) group. Also, the structure and properties of oligomer–metal complexes of OPAP with Cu(II), Ni(II), Zn(II), and Co(II) were studied. Antimicrobial activites of the oligomer and its oligomer–metal complexes were tested against B. cereus, L. monocytogenes, B. megaterium, B. subtilis, E. coli, Str. thermophilus, M. smegmatis, B. brevis, E. aeroginesa, P. vulgaris, M. luteus, S. aureus, and B. jeoreseens. Also, according to differential thermal analysis and thermogravimetric analysis, OPAP and its oligomer–metal complexes were stable throughout to temperature and thermo‐oxidative decomposition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2004–2013, 2002     

Starch‐g‐polycaprolactone copolymerization using diisocyanate intermediates and thermal characteristics of the copolymers

Starch‐g‐polycaprolactone copolymers were prepared by two‐step reactions. The diisocyanate‐terminated polycaprolactone (NCO–PCL) was prepared by introducing NCO on both hydroxyl ends of PCL using diisocyanates (DI) at a molar ratio between PCL and DI of 2:3. Then, the NCO–PCL was grafted onto corn starch at a weight ratio between starch and NCO–PCL of 2:1. The chemical structure of NCO–PCL and the starch‐g‐PCL copolymers were confirmed by using FTIR and ¹³C‐NMR spectrometers, and then the thermal characteristics of the copolymers were investigated by DSC and TGA. By introducing NCO to PCL (M_n : 1250), the melting temperature (T_m ) was reduced from 58 to 45°C. In addition, by grafting the NCO–PCL (35–38%) prepared with 2,4‐tolylene diisocyanate (TDI) or 4,4‐diphenylmethane diisocyanate (MDI) onto starch, the glass transition temperatures (T_g 's) of the copolymers were both 238°C. With hexamethylene diisocyanate (HDI), however, T_g was found to be 195°C. The initial thermal degradation temperature of the starch‐g‐PCL copolymers were higher than that of unreacted starch (320 versus 290°C) when MDI was used, whereas the copolymers prepared with TDI or HDI underwent little change. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 986–993, 2000     

Poly(dimethylsiloxane)urethane‐co‐poly(methyl methacrylate) with 2,4‐toluene diisocyanate and m‐xylene diisocyanate. I. Compatibility and impact strength of copolymers

In this study, slightly crosslinked poly(dimethylsiloxane)urethane‐co‐poly(methyl methacrylate) (PDMS urethane‐co‐PMMA) graft copolymers based on two diisocyanates, 2,4‐toluene diisocyanate (2,4‐TDI) and m‐xylene diisocyanate (m‐XDI), were successfully synthesized. Glass‐transition behaviors of the copolymers were investigated. Results confirm that PDMS–urethane and PMMA are miscible in the 2,4‐TDI system, but are only partially miscible in the m‐XDI system. The methylene groups adjoining the isocyanate in the m‐XDI system show increased phase‐separation behavior over the 2,4‐TDI system, in which the benzene ring adjoins the isocyanate. The functional group of PDMS–urethane improves the impact strength of the copolymers. The toughness depends on the compatibility of PDMS–urethane and PMMA segments in the copolymers. In the m‐XDI system, the impact strength of the copolymer containing 3.75 phr macromonomer achieves a maximum value (from 13.02 to 22.21 J/m). The fracture behavior and impact strength of the copolymers in the 2,4‐TDI system are similar to that of PMMA homopolymer, although they are independent of the macromonomer content in the copolymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1875–1885, 2002     

Synthesis,characterization and properties of functionalized styrene–maleimide copolymers

New functionalized styrene–maleimide copolymers were prepared by free radical copolymerization of styrene (St) and N‐4‐carboxybutylmaleimide (NBMI) in chloroform, using 2,2′‐azobisisobutyronitrile (AIBN) as initiator. Monomer and copolymer characterization was carried out by ¹H‐ and ¹³C‐NMR. Copolymer composition was determined by elemental analysis and Fourier‐transform infrared (FTIR) spectroscopy. The glass transition temperature (from DSC) and the thermogravimetric analysis (TGA) of the copolymers were consistent with the thermal behavior and stability observed for alternating St–maleimide copolymers. St–NBMI copolymers crosslinked with divinylbenzene (DVB) were also synthesized and their cation exchange properties evaluated in order to assess the capacity of the new copolymers to bind metallic ions. Copyright © 2005 Society of Chemical Industry     

Synthesis and comparative study of thermal stabilities of the imidization of some maleic anhydride copolymers

In the present study, first, maleic anhydride‐styrene (MA‐St), maleic anhydride‐allyl phenyl ether (MA‐APhE), maleic anhydride‐heptene‐1(MA‐Hp), and maleic anhydride‐allyl propionate (MA‐AP) copolymers have been synthesized in different solvents in the presence of azobisisobutyronitrile (AIBN) at 70°C. Then, these four copolymers have been reacted with aniline at 60°C in N,N‐dimethyl formamide (DMF), and maleamidic acid derivatives of these copolymers have been synthesized. Next, they have been obtained from their maleimide derivatives by heating under vacuum at 150°C. All these polymers have been characterized by Fourier Transform infrared spectroscopy (FTIR) and investigated their thermal properties by using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) methods. The analyses results showed that thermal properties of maleimide derivatives of maleic anhydride copolymers changed as depend on the neighbor monomers of maleic anhydride. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2250–2254, 2006     

Water‐soluble copolymers from functionalized monomers (sodium o‐ and p‐methacryloylaminophenylarsonate): Synthesis and characterization

Copolymers of sodium o‐methacryloylaminophenylarsonate (o‐MAPHA‐Na) 1 and p‐methacrylolylaminophenylarsonate (p‐MAPHA‐Na) 2 with sodium acrylate (AA‐Na) 3 , sodium methacrylate (AM‐Na) 4 and acrylamide (AAD) 5 were prepared by free radical polymerization in aqueous media at 70°C using potassium persulfate (K₂S₂O₈) as the initiator. The total monomer concentration was carried out at 0.5M and the feed ratio ( M₁ : M₂ ) was varied from 10 : 90 to 90 : 10 mol%. The kinetic study was carried out by dilatometric method. The copolymer compositions were calculated by arsenic content in the copolymers. The As content (ppm) was determined by atomic absorption spectrometry (AAS). The reactivity ratios (r₁, r₂) were estimated by the Kelen‐Tüdös linearization method as well as error‐in‐variables method using the computer program RREVM®. In all cases, r₁ < 1 and r₂ > 1, indicating a tendency to form random copolymers. The values suggest that the copolymers contain a larger proportion of comonomer (i.e., AA‐Na, AM‐Na, or AAD). Weight‐average molar masses (M _w) of copolymers were determined by multi‐angle light scattering. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Studies on the copolymerization of methyl methacrylate and N-aryl maleimides

This article describes the synthesis and characterization of copolymers of methyl methacrylate (MMA) and N-4-chlorophenyl maleimide (PC)/N-3-chlorophenyl maleimide (MC). The copolymers were synthesized by varying the mole fraction of N-aryl maleimides from 0.1 to 0.5 in the initial feed using azobisisobutyronitrile (AIBN) as an initiator and tetrahydrofuran (THF) as the solvent. The copolymer composition was determined from the ¹H-NMR spectra by taking the ratio of proton resonance signals due to methoxy protons (δ = 3.59 ppm) of MMA and aromatic protons (δ = 7.2–7.4 ppm) of N-aryl maleimides. The reactivity ratios for MMA–PC and MMA–MC copolymers were found to be 0.952 (r₁), 0.029 (r₂) and 0.833 (r₁) and 0.033 (r₂), respectively. Thermal characterization of the copolymers was done using differential scanning calorimetry (DSC) and dynamic thermo-gravimetry. Initial decomposition temperature and glass transition temperature increased with increasing mole fraction of N-aryl maleimide content in the copolymers. © 1996 John Wiley & Sons, Inc.     

Copolymerization of N‐aryl substituted itaconimide with methyl methacrylate: Effect of substituents on monomer reactivity ratio and thermal behavior

The article describes the synthesis and characterization of N‐(4‐methoxy‐3‐chlorophenyl) itaconimide (MCPI) and N‐(2‐methoxy‐5‐chlorophenyl) itaconimide (OMCPI) obtained by reacting itaconic anhydride with 4‐methoxy‐3‐chloroanisidine and 2‐methoxy‐5‐chloroanisidine, respectively. Structural and thermal characterization of MCPI and OMCPI monomers was done by using ¹H NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of MCPI or OMCPI with methyl methacrylate (MMA) in solution was carried out at 60°C using AIBN as an initiator and THF as solvent. Feed compositions having varying mole fractions of MCPI and OMCPI ranging from 0.1 to 0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by FTIR, ¹H NMR, and elemental analysis and percent nitrogen content was used to calculate the copolymer composition. The monomer reactivity ratios for MMA–MCPI copolymers were found to be r₁ (MMA) = 0.32 ± 0.03 and r₂ (MCPI) = 1.54 ± 0.05 and that for MMA–OMCPI copolymers were r₁ (MMA) = 0.15 ± 0.02 and r₂ (OMCPI) = 1.23 ± 0.18. The intrinsic viscosity [η] of the copolymers decreased with increasing mole fraction of MCPI/or OMCPI. The glass transition temperature as determined from DSC scans was found to increase with increasing amounts of OMPCI in copolymers. A significant improvement in the char yield as determined by thermogravimetry was observed upon copolymerization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2391–2398, 2006