Thermally resistant,mechanically stable,and processable triphenylamine-based hyperbranched copolyimides

A trifunctional, triamine 4-(4-aminophenoxy)-4′,4′′-diamino triphenylamine ( A ) was successfully synthesized by N-arylation in the presence of cesium fluoride, followed by catalytic reduction. A series of aromatic tree-shaped hyperbranched copolyimides (HBPIs, 1–4) was fruitfully synthesized by one-pot polycondensation of a newly synthesized triamine monomer (A), difunctional monomer 4,4′-dianiline, 4,4′-oxydianiline (ODA) and a series of aromatic dianhydride monomers. The appropriate molar ratio of triamine, ODA to the dianhydride monomer B is 1:1:2.5 for HBPIs synthesis using the A₂ A₃ B₅ type copolymerization approach. The synthesized HBPIs exhibited a moderate number-average molecular weight (25,700–28,400 g/mol) and polydispersity in the range 2.6–3.0 as revealed by gel permeation chromatography measurement. The oxidative thermal degradation analyses of the HBPIs showed that the synthesized materials are thermally stable up to 500°C and glass transition temperature in the range 290–302°C. The elongation at break was found in the range 4.8%–8.1% as revealed by tensile measurement. Besides, good thermal stability the HBPIs exhibited excellent flow, appreciable organosolubility, easy processability, and noticeable mechanical stability, thus suggesting their use as thermally resistant, protective coatings for various devices and outdoor environment in the future.     

Synthesis and characterization of novel photo‐crosslinkable fluorinated poly(phthalazinone ether)s for optical waveguides

A series of novel photo‐crosslinkable fluorinated poly(phthalazinone ether)s containing 1,1‐diphenylethylene segments in the polymer main chain, used for optical waveguide materials, were synthesized by polycondensation reaction of decafluorobiphenyl with a mixture of 4‐(4‐hydroxylphenyl)(2H)‐phthalazin‐1‐one (DHPZ), 4,4‐(hexafluoroisopropylidene)diphenol and 1,1‐bis(4‐hydroxyphenyl)ethylene (BHPE) as co‐reactant. The feed ratio of DHPZ to total bisphenols varied from 0 to 80 mol%, while that of BHPE remained at 20 mol% for all polymers. The obtained copolymers show good solubility in some common polar organic solvents. The resulting polymers were photo‐crosslinked after UV irradiation for 10 min in the presence of a photoinitiator. The cured polymers show good chemical resistance, high thermal stability (temperatures of 1% mass loss after curing of 472–496 °C under nitrogen) and high glass transition temperatures (160–249 °C) which could be further increased by about 10 °C after photochemical crosslinking. By adjusting the copolymerizing bisphenol content, the refractive indices of transverse electric and transverse magnetic modes (at 1550 nm) of films of the polymers were exactly tuned in the range 1.5029–1.5661 and 1.4950–1.5502, respectively. The propagation losses of the cured films were measured and found to be less than 0.3 dB cm^?1 at 1550 nm, indicating the promise of these materials for passive optical waveguide devices. Copyright © 2011 Society of Chemical Industry     

Synthesis and properties of novel hyperbranched polyimides end‐capped with metallophthalocyanines

A fluorinated hyperbranched polyimide (HBPI) is synthesized by using a triamine monomer, 1,3,5‐tris(2‐trifluoromethyl‐4‐aminophenoxy)benzene (TFAPOB) (B₃), as a “core” molecule, 4,4′‐oxydiphthalic anhydride (ODPA) as a A₂ monomer, and 4‐aminophthalonitrile as an end‐capping reagent. After that, a series of novel fluorinated hyperbranched polyimides end‐capped with metallophthalocyanines were prepared by the reactions of dicyanophenyl end‐capped hyperbranched polyimide with excessive amounts of 1,2‐dicyanobenzene and the corresponding metal salt in quinoline. The resulting polyimides containing metallophthalocyanine unites shows optical absorption in the visible region. The absorption bands of the polymers in chloroform solution are in the range of 665–701 nm. These polyimides show glass transition temperatures between 216 and 225°C, and the 5 wt % weight loss temperature of the polymers varied from 440 to 543°C under nitrogen. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,characterization and properties of TAP‐6FDA hyperbranched polyimides with different branching degrees

A series of hyperbranched polyimides were successfully synthesized by condensation polymerization of A₂‐type dianhydride monomer 2,2‐bis(3,4‐dicarboxylphenyl) hexafluoropropane dianhydride (6FDA) and B′B₂‐type triamine monomer 2,4,6‐triaminopyrimidine (TAP). Polymers with different branching degrees (DB) and terminated groups were obtained by changing the monomer addition order and the monomer molar ratio. Fourier transform infrared spectroscopy and ¹H NMR were used to verify the structure of the prepared polyimides, which indicated that the amino group still existed in all the products. The DB of the polymers indicated by ¹H NMR increased from 30% to 79% with the molar ratio of TAP:6FDA decreasing from 1:1 to 1:2. The absolute molecular weights were measured by size‐exclusion chromatography with multi‐angle laser light‐scattering detection, which suggested that the highest molecular weight would be obtained when the molar ratio of amino groups:anhydride groups of the monomers was 3:3.2. With the DB increasing, the d‐spacing values indicated by wide angle X‐ray diffraction increased from 5.15 Å to 5.68 Å and the UV ? visible spectra of the polymers exhibited decreasing cut‐off wavelengths. The 5% weight loss temperature in nitrogen increased with decreasing content of TAP monomer, and the glass transition temperatures of the obtained polyimides decreased from 282 °C to 258 °C with increasing DB. © 2013 Society of Chemical Industry     

Synthesis of UV‐curable hyperbranched polyurethane (meth)acrylate oligomers via thiol‐ene “click” chemistry

First, the second‐generation hyperbranched poly(amine‐ester) (G2‐OH) was successfully prepared by thiol‐ene “click” chemistry. Subsequently, a series of photosensitive hyperbranched oligomers (G2‐ORs) were synthesized by facile modifications of the G2‐OH with acryloyl chloride, methacryloyl chloride, IPDI‐HEA, and IPDI‐HEMA, respectively. The structures of hyperbranched oligomers were characterized by element analysis, FT‐IR, ¹H NMR, GPC and viscosity measurement. It was shown that these synthesized oligomers have narrow molecular weight distribution and low intrinsic viscosity at 30°C. UV–vis spectra results showed that the G2‐ORs had sharp absorption bands at around 202 nm. The results of photosensitivities measurement indicated that the G2‐Macr shows the highest photosensitive than other hyperbranched oligomers in the absence of photoinitiator. In addition, these UV‐cured photosensitive G2‐ORs had good thermal properties. The solubilities of the synthesized hyperbranched oligomers were also examined. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nano‐scaled ordering of hyperbranched and star‐hyperbranched polymers

Hyperbranched polystyrenes (HPS) were prepared by living radical polymerization of 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC) as an inimer under UV irradiation. These HPS exhibited large amounts of photofunctional diethyldithiocarbamate (DC) groups on their outside surfaces. We derived star‐HPS (SHPS) by grafting from such HPS macroinitiator with methyl methacrylate (MMA) or ethyl methacrylate (EMA). The ratios of radius of gyration to hydrodynamic radius R_g/R_h for HPS and SHPS in tetrahydrofuran (THF) were in the range of 0.74–0.90 and 1.05–1.12, respectively. HPS and SHPS behaved in a good solvent as hard and soft spheres, respectively. We demonstrated the structural ordering of both branched polymers in THF through small‐angle X‐ray scattering (SAXS), by varying the polymer concentration. As a result, HPS and SHPS formed face‐centered‐cubic (fcc) and body‐centered‐cubic (bcc) structures, respectively, near the overlap threshold (C*). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3340–3345, 2006     

Gas permeability of fluorinated hyperbranched polyimide

The gas permeability of carbon dioxide, oxygen and nitrogen for hyperbranched polyimide (HBPI) containing trifluoromethyl groups were investigated. The HBPIs were prepared by condensation polymerization of a triamine monomer, 1,3,5‐tris(2‐trifluoromethyl‐4‐aminophenoxy) benzene (TFAPOB) and a commercially available dianhydride monomer 1,4‐bis(3,4‐dicarboxyphenoxy) benzene dianhydride (HQDPA). With different monomer addition methods and different monomer molar ratios, amine terminated HBPI (AM‐HQDPA) and anhydride terminated HBPI (AD‐HQDPA) were obtained, subsequently, the trifluoromethylphenyl amine terminated HBPI (CF₃‐HQDPA) was achieved by modifying the end groups of AD‐HQDPA with (3,5‐ditrifluoromethyl)aniline. The CF₃‐HQDPA exhibited a good mechanical and thermal stability as well as AM‐HQDPA, and showed better gas permeabilities than that of AM‐HQDPA because of increase of free volume contributed by the bulky trifluoromethyl group introduced, but, the selectivity ofCF₃‐HQDPA was lower than that of AM‐HQDPA. This result was consistent with the trade‐off relationship. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and application of water‐soluble hyperbranched poly(ester)s from maleic anhydride and glycerol

A water‐soluble hyperbranched polyester with a considerable number of hydroxyl terminal groups was synthesized by reacting maleic anhydride and glycerol in the absence of a solvent. The synthesized intermediate product was converted to the hyperbranched polyester by condensation polymerization, and the water by‐product produced during the esterification reaction may be removed by vacuum distillation. In the synthesis process, the crosslinking reaction occurs readily if maleic anhydride is in excess. The result shows that the product synthesized by this one‐step method is insoluble in water at room temperature, whereas the product of a quasi one‐step method, in which pentaerythritol was added as a core molecule, has good water solubility when pentaerythritol and the raw material have a molar ratio of 1 : 100 or 1 : 150. The resulting hyperbranched polyester was purified by column chromatography and characterized by infrared spectrometry. The synthetic hyperbranched polyester was used at 0.5% as a crosslinking agent for acrylic ester to inform acrylic ester latex film; the water absorption of the film was decreased significantly, the viscosity was increased, and some mechanical properties were improved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crosslinkable fluorinated hyperbranched polyimide for thermo‐optic switches with high thermal stability

A series of fluorinated hyperbranched polyimides (FHBPIs) were synthesized by condensation of a triamine monomer, 1,3,5‐tris(2‐trifluoromethyl‐4‐minopheoxy) benzene (TFAPOB) and various aromatic dianhydride monomers with different linear length for application on integrated optical devices. Near infrared absorption measurement shows that it has high transparency in optical communication wavelength region. The glass transition temperature and thermal decomposition temperature were 189°C and 596°C, respectively. According to the atomic force microscopy analysis, the surface roughness of the FHBPI films is 0.208 nm. A classic Mach–Zehnder interferometer thermo‐optic switch with single mode waveguide fabricated by FHBPIs represents excellent switching characteristic. The rise time and fall time of this device are 530 µs for both. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Sulfur‐containing copolyimides for the membrane‐based separation of aromatic/aliphatic mixtures

Recently, sulfur‐containing copolyimides have attracted increasing attention as membrane materials for the separation of gaseous, vaporous, or liquid mixtures because of their superior separation properties. Therefore, a novel sulfur‐containing copolyimide based on 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐diaminodiphenylsulfide, and 3,5‐diaminobenzoic acid was synthesized, characterized, and extensively investigated in toluene/n‐decane pervaporation experiments. To characterize the separation properties of the copolyimide, the flux and selectivity were determined with separation mixtures between 60 and 80 wt % toluene. The separation temperature was varied between 70 and 110°C. Thereby, we observed that when the temperature was increased from 70 to 90°C, the flux and selectivity did not change significantly. In contrast, a temperature change from 90 to 110°C caused an extensive increase in the flux. The most significant change was found for an 80 wt % toluene mixture, where an increase from 1.9 to 7 kg·μm·m^?2·h^?1 was observed. Simultaneously, the selectivity which is a measure of the quality of the separation (α) decreased from α = 11.8 to α = 9.3. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of allyl‐ended hyperbranched organic silicone resin by halloysite‐supported platinum catalyst

A novel allyl‐ended hyperbranched organic silicone resin (AHSR) was prepared successfully by hydrosilylation between phenyltriallylsilane and 1,1,3,3‐tetramethyl disiloxane with halloysite‐supported platinum (Pt–halloysite) as the catalyst. The chemical structure of the AHSR was characterized by ¹H‐NMR and Fourier transform infrared spectroscopy, and its molecular weight was determined by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. The Pt–halloysite catalyst was prepared from chloroplatinic acid and halloysite by the simple wet impregnation method. The transmission electron micrographs of the catalyst showed that the platinum dispersed homogeneously into the halloysite nanotubes. Compared with the traditional homogeneous Speier and Karstedt catalysts, our heterogeneous Pt–halloysite catalyst demonstrated a higher catalytic activity, which was confirmed by IR monitoring of the attenuation of the Si? H stretching band. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of s‐triazine‐based hyperbranched polyurethane for novel carbon‐nanotube‐dispersed nanocomposites

s‐Triazine‐based hyperbranched polyurethanes (HBPUs) with different hard segments were synthesized by A₂ + B₃ approach. Various kinds of multiwalled carbon nanotube (MWNT) nanocomposites with HBPU were prepared to investigate an impact of hyperbranched polymer on dispersion of MWNTs in the polymer matrix and the resulting properties of nanocomposites. Synthesized HBPUs were characterized using FTIR and NMR measurements. The highly branched structures were found very effective in enhancing the pristine MWNT dispersion in the polymer matrix. As a result, the MWNT‐reinforced HBPU nanocomposites showed a steep increase in the yield stress and modulus and enhanced shape memory effect with an increase of hard segment and MWNT loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of biodegradable linear–hyperbranched barbell‐like poly(ethylene glycol)‐supported poly(lactic‐ran‐glycolic acid) copolymers through direct polycondensation

A series of biodegradable linear–hyperbranched barbell‐like poly(ethylene glycol) (PEG)‐supported poly(lactic‐ran‐glycolic acid) (PLGA) copolymers were synthesized with PEG, d ,l ‐lactic acid aqueous solution, glycolic acid and gluconic acid (Glu) under bulk conditions. The branching density of the hyperbranched section was varied by controlling the molar ratio of Glu to hydroxyl‐terminal groups of PEG ([Glu]/[OH] = 1, 3.5, 6.0, 8.5). Chemical structures of these copolymers were confirmed using NMR spectroscopy. The molecular weights were determined using ¹H NMR group analysis and gel permeation chromatography, both results being consistent with one another. The results of hydrolytic degradation indicate that these copolymers can degrade completely in no more than three weeks. The thermal properties were evaluated using differential scanning calorimetry and thermogravimetric analysis. The results indicate that the glass transition temperatures and melt temperatures of these copolymers are not above 50 °C. The self‐assembly behavior of the copolymers on hydrophilic surfaces was also investigated. The morphology of self‐assembly films made of the copolymers was observed using atomic force microscopy, and the results indicate that these copolymers exhibit more inhomogeneous and rough structural orientated films on a silicon wafer substrate with increasing branching densities. Due to the favorable biodegradability and biocompatibility of the PLGA and PEG, the results suggest new possibilities for these novel structural amphiphilic linear–hyperbranched barbell‐like copolymers as potential biomaterials. © 2013 Society of Chemical Industry     

Synthesis and characterization of organo‐soluble fluorinated polyimides

A novel fluorinated diamine monomer with a keto group, 4‐[4‐amino‐2‐trifluoromethyl phenoxy]‐4′‐[4‐aminophenoxy]benzophenone (ATAB) was prepared by reacting dihydroxybenzophenone with 4‐chloronitrobenzene and 2‐chloro‐5‐nitrotrifluoromethylbenzene in the presence of potassium carbonate followed by catalytic reduction with palladized carbon (10%). Fluorinated polyimides IVa–e were synthesized from the diamine mentioned above via a two‐step method (thermal and chemical imidization). Polyimides IVa–e have inherent viscosities in the range 0.65–1.06 dL g^?1 (thermal imidization) and 0.82–1.56 dL g^?1 (chemical imidization). The polyimides prepared by chemical imidization exhibit excellent solubility. Polyimide films exhibit tensile strength, elongation and tensile modulus in the ranges 96–106 MPa, 9–13% and 1.1–1.7 GPa, respectively. The T₁₀ values of the polyimides are in the range 540–598 °C in nitrogen and 545–586 °C in air, with more than 50–60% char yield. They have T_g values between 244 and 285 °C. The prepared polyimides show cut‐off wavelengths in the range 365–412 nm and transmittance at 450 nm in the range 80.9–94.2%. The dielectric constants of the polyimide films are in the range 3.10–3.77 at 1 kHz and 3.04–3.66 at 10 kHz, with moisture absorption of 0.14–0.40%. Copyright © 2006 Society of Chemical Industry     

Solution properties of hyperbranched polymers and synthetic application for amphiphilic star‐hyperbranched copolymers by grafting from hyperbranched macroinitiator

Hyperbranched polystyrenes (PS) were prepared by living radical photopolymerization of N,N‐diethyldithiocarbamoylmethylstyrene (DTCS) as an inimer under UV irradiation. Branched PS with an average chain length between branching points of four styrene units was also prepared by living radical copolymerization of DTCS with styrene. The ratio of radius of gyration to hydrodynamic radius R_G/R_H for these hyperbranched polymers was in the range 0.82–0.89 in toluene. The translational diffusion coefficient D(C) showed a constant value in the range of 0–14 × 10^?3 g ml^?1 in toluene. It was found from these dilute solution properties that hyperbranched PSs formed a unimolecular structure even in a good solvent because of their compact nature. These hyperbranched PSs exhibited large amounts of photofunctional carbamate (DC) groups on their outside surfaces. Subsequently, we derived amphiphilic star‐hyperbranched copolymers by grafting from hyperbranched macroinitiator with 1‐vinyl‐2‐pyrrolidinone. These star‐hyperbranched copolymers were soluble in water and methanol. © 2001 Society of Chemical Industry     

Synthesis and characterization of photo‐crosslinkable polyfluorene with acrylate side‐chains

A photo‐crosslinkable polymer, poly[2,7‐(9,9‐dioctylfluorene)‐co‐2,7‐(9‐hexyl‐9‐(2‐acrylate ethyl)‐9H‐fluorene)] (P3), was synthesized and the photo‐crosslinkable acrylate groups were introduced into the side‐chains of the polyfluorene derivative after its polymerization. This method avoids the possible crosslinkage of the crosslinkable groups on the monomers during polymerization in the traditional synthesis route by the polymerization of the monomers with the crosslinkable side‐chains. The soluble and processable polymer P3 could be crosslinked via the acrylate groups in its side‐chains upon exposure to UV light in nitrogen atmosphere. The crosslinking was confirmed by IR spectroscopy: the IR peak of C?C bond at 1635 cm^?1 decreased and that of the vinyl C? H bond at 742 cm^?1 disappeared after the UV exposure. The absorption spectra of P3 remain unchanged after crosslinking, but a longer wavelength emission at 517 nm appeared in the photoluminescent and electroluminescent spectra of the crosslinked P3, which could be attributed to the formation of keto defects during the photo crosslinking. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2336–2342, 2006     

Dielectric properties and solubility of multilayer hyperbranched polyimide/polyhedral oligomeric silsesquioxane nanocomposites

Multilayer hyperbranched polyimide/polyhedral oligomeric silsesquioxane (POSS) nanocomposites were synthesized by the reaction of a bromide‐hyperbranched polyether/POSS and a main‐chain polyimide containing hydroxyl‐functional groups. The first layer was formed through the direct reactions of the main‐chain hydroxyl groups with monochloroisobutyl polyhedral oligomeric silsesquioxane (POSS–Cl). The second and third layers were prepared by the repeated reactions of bromine ether branches that incorporated POSS–Cl with 3,5‐dihydroxybenzyl alcohol. Regardless of the fixed amount of POSS, the higher layers yielded lower dielectric constants. Even when the amount of the POSS loading was reduced 4‐fold, the third layer still had the lowest dielectric constants. The lowest dielectric constant of 2.54 was found in the third layer of the hyperbranched polyimide/POSS nanocomposite because of the large free volume and loose polyimide structures. The densities of the hyperbranched polyimide/POSS nanocomposite corresponded to the dielectric constants. The lower the density was, the higher the free volume was and the lower the dielectric constant was. The experimental results indicated that the hyperbranched polyimide/POSS nanocomposite exhibited increased solubility in comparison with pure polyimide. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of partially conjugated hyperbranched light‐emitting polymers

Via A₂ + B₄ and A₂ + B₃ [where A₂ is 1,4‐distyrylol‐2,5‐butoxybenzene, B₃ is 1,1,1‐tris‐(p‐tosyloxymethyl)‐propane, and B₄ is pentaerythritol tetra(methyl benzene sulfonate)] approaches, we synthesized two kinds of partially conjugated hyperbranched polymers, hyperbranched polymer with 3 arms (HP1) and hyperbranched polymer with 4 arms (HP2), which had rigid conjugated segments [oligo‐poly(phenylene vinylene)] and flexible, nonconjugated spacers arranged alternately through ether bonds in the skeleton. The conjugated segments were modified by pendant butoxy groups, which imparted the resulting polymers with excellent solubility in common organic solvents and excellent film‐forming abilities. Fourier transform infrared and nuclear magnetic resonance spectroscopy were used to identify the structure of the monomers and polymers. Thermal property investigations showed that two polymers both had good thermal stability with their decomposition temperatures in the range 396–405°C and high glass‐transition temperatures, which are of benefit to the fabrication of high‐performance light‐emitting devices. The photophysical properties were studied, and the relative photoluminescence quantum efficiencies of HP1 and HP2 in dilute chloroform solution amounted to 56.8 and 49.3%, respectively. A brief light‐emitting diode device with a configuration of indium tin oxide/HP1/Ca/Al was fabricated, and its electroluminescence performance was studied. The brightness of the device reached an optimistic maximum of 190 cd/m² at 8.2 V. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of new amphiphilic water‐stable hyperbranched polycarbosilane polymers

New amphiphilic hyperbranched polymers possessing hydrophobic skeletons and hydrophilic terminal groups have been prepared and characterized. The synthetic strategy involved the formation of a new stable matrix with aromatic units within a carbosilane backbone, as well as the use of a classical polycarbosilane matrix. Both of them with allyl groups on the surface have narrow polydispersity values. Molecular weight and polydispersity of the hyperbranched polymers were obtained using gel permeation chromatography with multi‐angle light scattering, and determination of the average number of functional groups present on the surface was achieved using ¹H NMR spectroscopy. The introduction of ionic groups was carried out via thiol–ene reactions with various thiol derivatives. The thermal properties of the polymers were also analysed using differential scanning calorimetry and zeta potential measurements. © 2013 Society of Chemical Industry     

Synthesis and properties of self‐crosslinkable polyurethane–urea with silsesquioxane formation

Based on the typical two‐step polyurethane–urea synthesis, a new series of self‐crosslinkable polyurethane (PU)–urea formulations, consisting of poly(tetramethylene oxide) and 4,4′‐diphenyl methane diisocyanate, and extended by ethylenediamine (EDA)/aminoethylaminopropyltrimethyoxysilane (AEAPS), were prepared. FTIR, ESCA, WAXD, DSC, and mechanical properties of samples were recorded. The results show that the self‐crosslinkable polyurethane–urea could be crosslinked by hydrolysis of the trimethyloxysiloxane group to form the silsesquioxane structure. These structures represent a kind of nanosize, cagelike, chemical crosslink site as well as filler, which affect the properties of PU. The morphology, varied with different ratios of EDA/AEAPS, was also discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 190–195, 2004