bluuebunny/crossref_metadata_2025_split huggingface dataset:
Nomenclature of polymers (based on structure)
Authors: Sengupta Tapan Kumar 
Published: April 2003

AbstractIn the complete absence of a systematic polymer nomenclature, a scheme of nomenclature based on structure is proposed. The problem of naming a “mer” has been solved for an addition polymer by adding “ne” to the monomer name, the justification being on withdrawal of a π bond a monomer becomes a mer. To furnish completeness to the nomenclature, condensation polymers were included in the system. The present nomenclature system of polymers is very arbitrary. Some polymers are not chemically named, some named incorrectly, and there are some fantastic names. After pointing these out, the possible solutions were shown, encompassing a systematic discussion on nearly every type of polymer–linear, branched, or crosslinked–and copolymer (including block or graft), and plastic, fiber, or rubber, and stereospecific polymer. One or more names were proposed for different cases.
13C‐NMR study of cellulose derivatives in the solid state
Authors: Hoshino M. , Takai M. , Fukuda K. , Imura K. , Hayashi J. 
Published: April 2003

AbstractThe application of NMR for natural organic compounds has been carried out from the early history of NMR. But they reported on the liquid state NMR and the samples were limited to the materials which dissolved in proper solvents. It has been possible to measure the samples in the solid state in 1970s and is widely used as a familiar analytical method in 1980s. Whereas some of the data is inadequate, concerning cellulose derivatives, in particular, only nitrate and acetate were reported by Patterson1 and Doyle,2 respectively. In this paper, the 13C CP/MAS solid state NMR spectra of several cellulose derivatives are shown and the relationship between the structure and spectrum is discussed.
A novel insertion reaction of epoxy compounds into phenyl ester linkages in polymer chains
Authors: Nishikubo Tadatomi , Shimokawa Tutomu , Hirano Toshiyuki , Shiina Atushi 
Published: April 2003

AbstractThe insertion reaction of various epoxy compounds such as phenyl glycidyl ether (PGE), methyl glycidyl ether, butyl glycidyl ether (BGE), and styrene oxide into the phenyl ester linkage in the polymer chain was investigated using quaternary ammonium salts as catalysts in diglyme, anisole, sulfolane, o‐dichlorobenzene, or DMSO at 100–150°C. The reaction of PGE with poly[4‐(4‐nitrobenzoyloxy)styrene] (polymer 1a) proceeded almost quantitatively to give the corresponding polymer using tetrabutylammonium bromide (TBAB) as catalyst in diglyme at 100°C for 24 h. The reactions of BGE with poly(4‐nitrophenyl methacrylate), and copolyarylate derived from 2,2‐bis(4‐hydroxyphenyl)‐1,1,1,3,3,3‐hexafluoropropane and iso‐ and terephthaloyl chlorides also produced the corresponding polymers with 86 and 89 mol% new structural units, respectively, using TBAB in sulfolane at 150°C for 24 h. Furthermore, it was found that the degree of insertion of the epoxy compound into the ester linkage in the polymer chain was affected by the kind of epoxy compound, reaction solvent, catalyst concentration, substituent group on the phenyl ester, and structure of the polymer. Chiral polymers were also synthesized with high degrees of insertion by the reaction of chiral epoxides such as (R)‐1,2‐epoxyhexane, (R)‐1,2‐epoxyheptane, and (R)‐1,2‐epoxydecane with polymer 1a and poly(2,4‐dichlorophenyl methacrylate) using TBAB in diglyme at 120°C for 24 h.
Functional metallomacrocycles and their polymers. XXII. Thermally stable metallophthalocyanine formaldehyde condensation resins
Authors: Itoh H. , Masuda E. , Koyama T. , Hanabusa K. , Shirai H. , Kurose A. , Takemoto K. 
Published: April 2003

AbstractA novel class of urea‐formaldehyde condensation resins containing covalently bound metallophthalocyanine [M = A1(III), Co(II), Ni(II), or Cu(II)] was synthesized from [tetrakis(methyl‐olamide)phthalocyaninato] metal complexes and dimethylolurea in aqueous solution by heating at 120°C for 10 h, followed by heating at 150°C for about 1 day. The structures of the polymers obtained were characterized by infrared and reflection electronic spectra. The thermal stabilities of the resins were evaluated by dynamic thermogravimetric analyses. The resin containing 21.3 wt % Ni(II)‐metallophthalocyanine had the greatest thermal stability, with 82 wt‐% char yield at 600°C in air atmosphere.
Thermal decomposition processes in aromatic polythiocarbonates
Authors: Montaudo Giorgio , Puglisi Concetto , Berti Corrado , Marianucci Elisabetta , Pilati Francesco 
Published: April 2003

AbstractThe thermal degradation of some polythiocarbonates obtained from bisphenol A bischloroformate and dithiols have been investigated by thermogravimetry and by direct pyrolysis in the mass spectrometer operating both in electron and chemical ionization. Poly(bisphenol A‐co‐tri‐methylenedithiocarbonate) decomposes by an intramolecular exchange process (back‐biting) producing trimethylene‐1,3‐dithiocarbonate and bisphenol A polycarbonate. The latter undergoes further thermal degradation at higher temperature yielding cyclic oligomers. Polymers containing tetramethylene‐1,4‐dithiocarbonate and hexamethylene‐1,6‐dithiocarbonate units decompose by the same mechanism, but the elimination of the dithiocarbonate units is not as fast and selective as the previous case. Some bisphenol A units are eliminated in the first thermal degradation stage and a rearrangement reaction producing ether linkage also occurs. Poly(phenylene‐1,3‐dithiocarbonate) decomposes by CO and COS loss with formation of sulfide and disulfide bridges along the polymer chains, which undergo further thermal degradation by a back‐biting process yielding a series of cyclic compounds. The thermal degradation of Poly(bisphenol A‐co‐phenylenedithiocarbonate) takes place through an interchange reaction producing phenylene‐1,3‐dithiocarbonate sequences which further decompose as the corresponding polymer. The remaining bisphenol A polycarbonate decomposes at higher temperature producing cyclic carbonates.
Synthesis and characterization of poly[N‐((10‐phenothiazinyl)‐6‐hexanoyl)ethylenimine] and N,N‐diethyl‐6‐(10‐phenothiazinyl)‐hexanamide
Authors: Kim Jinbaek , Litt Morton H. 
Published: April 2003

AbstractA new oxazoline monomer was made containing a chloroalkyl substituent which can be transformed to other functional groups by nucleophilic substitution. Oxazoline monomer containing the N‐phenothiazinyl substituent was made by reacting lithiated phenothiazine with the chloroalkyl substituted oxazoline and subsequently polymerized. N,N‐diethyl‐6‐chlorohexanamide was synthesized and N,N‐diethyl‐6‐(10‐phenothiazinyl)‐hexanamide, a model compound for the phenothiazine polymer, was made by reacting lithiated phenothiazine with this chloroamide. TCNQ did not complex with the polymer. The iodine and perchlorate complexes of the phenothiazine polymer had conductivities of 4.4 × 10 −8 and 6.9 × 10−6 S/cm, respectively, at room temperature. Each of these are higher than the corresponding values reported for complexes of the analogous model compounds or 3‐substituted phenothiazine polymer reported earlier.13, 22 This was attributed to the very short chain repeat distance for the present, symmetrically substituted polymer.
Structural aspects of polyimides. I. Polymerization and degradation of endo‐N‐phenylnadimide and endo‐N‐isobutylnadimide
Authors: Vijayakumar C. T. , Lederer K. , Kramer A. 
Published: April 2003

AbstractThe isomerization, polymerization, and degradation aspects of endo‐N‐phenylnadimide and endo‐N‐isobutylnadimide (NPNI‐N and NIBNI‐N) were investigated using infrared analysis (IR), differential thermal analysis (DTA), gel permeation chromatography (GPC), thermogravimetric analysis (TG), and capillary gas chromatography‐mass spectroscopic (GC–MS) techniques. Although the endotherm related to the retro‐Diels–Alder reaction is not registered in the DTA thermographs, on‐line mass spectrometric studies revealed the occurrence of this process. The formation of the Diels–Alder adduct of cyclopentadiene with N‐isobutylnadimide (NIBNI) during the polymerization of NIBNI‐N is proved. GPC studies on NPNI‐N and NIBNI‐N cured at 300°C for 3.0 h showed the average degree of polymerization to be three to four. The polymers obtained by curing NPNI‐N and NIBNI‐N at 300°C for 3.0 h showed 109.8 kJ/mol as the activation energy for degradation. The dynamic and isothermal pyrolysis studies clearly indicated the presence of intact norbornyl units in the polymer, and the breakage of CH2 bridges in the strained norbornyl structural elements was found to be the point of aromatization during degradation.
Thermal deesterification and decarboxylation of alternating copolymers of styrene with β‐substituted t‐butyl α‐cyanoacrylates
Authors: Ito Hiroshi , Padias Anne B. , Hall H. K. 
Published: April 2003

AbstractAlternating copolymers of styrene with β‐carboalkoxy‐substituted t‐butyl α‐cyanoacrylates undergo facile deesterification at 150–190°C, about 60°C below the deprotection temperature of poly(t‐butyl methacrylate), and decarboxylation at 170–200°C. When the β‐substituent is a methyl ester, the two events are clearly separated, with the deesterification occurring at a maximum rate at 165°C and decarboxylation at 193°C. Anhydride formation is negligible in this case. The copolymer with t‐butyl cyanofumarate exhibits simultaneous deesterification and decarboxylation events at 180°C with concomitant minor dehydration.
A rapid method for the determination of Mark–Houwink constants from GPC and viscosity data on a single sample
Authors: Price G. J. , Moore J. W. , Guillet J. E. 
Published: April 2003

AbstractA straightforward and rapid method for the determination of Mark–Houwink constants from GPC and viscometry is described. A single original polymer is sufficient since other samples were prepared by sonication. The use of a number of samples in this way is shown to improve the accuracy over determinations where only two polymer samples are used.
Zerovalent metal polymer composites. I. Metallized beads
Authors: Warshawsky A. , Upson D. A. 
Published: April 2003

AbstractBinding of a noble metal salt, e.g., PdCl to a functional ligand on a polymer surface, e.g., amine, quaternary ammonium, sulphonic acid, followed by reduction to zerovalent state and subsequent reductive deposition of transition metal ions, such as copper, nickel, and cobalt, provides a sequence of events leading to controlled zerovalent metal polymer composites. Metallization of submicron and larger beads are described. Large amounts of metal can be incorporated. The metallized beads retain the shape of the starting beads, even at high bonding of metal. They adapt the properties of the metal, e.g., magnetic properties. The submicron particles are sensitive to hydrolysis. Multicomponent systems, such as multimetallic beads, are provided by additive codeposition of metal ions, or by codeposition of metal and dye. Direct deposition of metal to preimmobilized dye ligands is also possible, leading to magenta, cyan, or yellow metallic beads, with no adverse influence on the magnetic properties. Further deposition of noble metals by subtractive deposition on active metal surfaces is also described. Submicron latices can be immobilized by coating on polyester‐based films, e.g., KODAK ESTAR base, and then activated with palladium and metallized to form highly conductive film surfaces.
The products of the reaction of polyphenylene sulfide with SO3 and SOCl2
Authors: Montoneri E. 
Published: April 2003

AbstractTwo polymer fractions, respectively with 28–38% and 6–9% sulphonated (SO3H) phenylene rings, may be isolated in the solid‐liquid reaction between p‐polyphenylene sulfide and SO3 in refluxing dichloroethane‐liquid SO2. The products relative yield depends on the experimental conditions of the reaction. No solvent has been found for these polymers.The reaction of the sulphonated polymers with SOCl2 leads to formation of higher substitution products containing both and functional groups. The polymers in chlorophenyl phenylsulphonylchloride form are soluble in excess SOCl2 and/or CHCl3, depending upon the concentration of ring chlorine.The mechanism of sulphonation in the heterogeneous medium and the presence of cross‐links in the reaction products are discussed.
Ring‐opening polymerization of 1‐(p‐substituted phenyl)‐2‐vinylcyclopropanes by Ziegler–Natta catalysts
Authors: Cho Iwhan , Song Soo Suk 
Published: April 2003

Abstract1‐(p‐Substituted phenyl)‐2‐vinylcyclopropanes such as 1‐phenyl‐2‐vinylcyclopropane (Ia), 1‐(p‐chlorophenyl)‐2‐vinylcyclopropane (Ib), 1‐(p‐anisyl)‐2‐vinylcyclopropane (Ic), and 1‐(p‐tolyl)‐2‐vinylcyclopropane (Id) were prepared and polymerized radically, cationically and with Ziegler–Natta catalysts. Ia and Ib polymerized exclusively in 1,5‐fashion with radical initiators. However, Ic and Id polymerized in 1,5‐fashion only with Ziegler–Natta catalysts. All polymers were soluble in ordinary organic solvent and solution‐cast films were clear and flexible, showing Tg values in the range of 39–71°C. Spectral data indicated that the double bonds of the polymer chains were in trans form in all cases. The difference between the polymerizabilities of different monomers are interpreted in terms of electronic properties of substituents.
Attaching chelating ligands to polybenzimidazole via epoxidation to obtain metal selective sorbents
Authors: Chanda M. , Rempel G. L. 
Published: April 2003

AbstractMicroporous polybenzimidazole of 250–500 μm spherical bead size from Celanese has been reacted with epichlorohydrin and sodium hydroxide and the resulting product with pendant epoxy groups has been reacted with various chelating ligands in order to augment the metal sorption capacity and selectivity of the resin. The chelating ligands used include ethylenediamine, diethylenetriamine, diethanolamine, dimethylglyoxime, L‐cysteine, thiourea, dithiooxamide, glyoxal‐bis‐2‐hydroxyanil, salicylaldehyde‐ethylenediimine, and glyoxal‐bis‐2‐mercaptoanil. The aminolysis of the pendant epoxy groups with the oligoamines has been performed in pyridine under reflux conditions, while the addition reactions with the other ligands which are alkali soluble have been carried out at room temperature in a mixture of dioxane and aqueous KOH using tetra‐n‐butylammonium iodide as the phase transfer catalyst. The products are found to possess high capacity and selectivity in metal sorption depending on the ligand attached.
Preparation and properties of fluorine‐containing aromatic polyamides from tetrafluorophthaloyl chlorides and aromatic diamines
Authors: Oishi Yoshiyuki , Harada Shigeyuki , Kamimoto Masa‐Aki , Imai Yoshio 
Published: April 2003

AbstractNew fluorine‐containing aromatic polyamides with inherent viscosities of 0.4–1.8 dL/g were prepared by the low temperature solution polycondensation of tetrafluoroisophthaloyl and tetrafluoroterephthaloyl chlorides with N,N′‐bis(trimethylsilyl)‐substituted aromatic diamines. The aromatic polyperfluoroisophthalamides were amorphous polymers with glass transition temperatures around 280°C, whereas the polyperfluoroterephthalamides were crystalline. Most of these aromatic polyamides were soluble in organic solvents, and began to decompose around 330°C in air or nitrogen atmosphere.
Investigation of the formation of poly(ethylene terephthalate) with model molecules. III. Metal‐catalyzed esterification and alcoholysis reactions: Influence of the structure of the reactants and of the nature of the reaction medium
Authors: Otton Jean , Ratton Serge , Vasnev Valerii A. , Markova Gali D. , Nametov Kahirman M. , Bakhmutov Vladimir I. , Vinogradova Svetlana V. , Korshak Vasilii V. 
Published: April 2003

AbstractWith a reaction conducted on model molecules with low amounts of catalysts and at low temperatures (170–225°C), it was shown that esterification is mainly catalyzed by the carboxylic acid groups and by the titanium derivatives; the activity of the other metals can only be seen when the concentration in carboxylic acid groups is low. In the alcoholysis reaction, the activity of Zn, Mn, and (much less) Ti, decreases when the percentage of ester in the reaction medium decreases, whereas it is the opposite with Sb. Moreover, Zn, Mn, and Co are sensitive to trace amounts of carboxylic groups (their activity decreases), whereas Ti is much less affected.
Syntheses of 4‐methacryloxy‐2,3,5,6‐tetrabromobenzyl phosphonates and effects of flame retardancy on their Co‐PMMA
Authors: Yang Chin‐Ping , Wang Sheng‐Sung 
Published: April 2003

Abstract4‐Methacryloxy‐2,3,5,6‐tetrabromobenzyl phosphonates (MTBBP) are prepared by the reaction of corresponding 4‐hydroxy‐2,3,5,6‐tetrabromobenzyl phosphonates (HTBBP) with methacryloyl chloride. Comparisons of flame retardancy among the copolymers of methylmethacrylate (MMA) with MTBBP or with 4‐methacryloxy‐2,3,5,6‐tetrabromotoluene(MTBT) and the mixture of poly(methyl methacrylate) (PMMA) with triphenyl phosphite reveal that the combination of phosphorus and bromine elements produces a synergistic effect on flame retardancy, and the chemical grafting of the fire‐resistant elements into the polymer backbone gives a better effect than the physical mixing of their compounds with polymer. The unsatisfactory results of homopolymers of the synthesized methacrylate monomers prepared by free radical polymerization in solution may be due to their less reactivities; however, they can readily copolymerize with a liquid vinyl monomer such as MMA by means of bulk polymerization.
The free radical distribution in emulsion polymerization using oil‐soluble initiators
Authors: Asua J. M. , Rodriguez V. S. , Sudol E. D. , El‐Aasser M. S. 
Published: April 2003

AbstractA new approach is presented to calculate both the distribution of particles with iradicals and the average number of radicals per particle in emulsion polymerizations carried out using oil‐soluble initiators. The convergence and accuracy of the approach were examined. It was found that, in agreement with previously published experimental results, the present approach predicts a kinetic behavior similar to that found for water‐soluble initiators. This effect is primarily due to the desorption of initiator radicals from the polymer particles rather than the contribution of the fraction of oil‐soluble initiator dissolved in the aqueous phase.
A study on the plasma polymerization of some cyano‐containing compounds and their electrical properties
Authors: Osada Y. , Yu Q. S. , Yasunaga H. , Kagami Y. , Wang F. S. , Chen J. 
Published: April 2003

AbstractPlasma polymerization of some cyano‐containing organic compounds was carried out at 13.56 MHz from the gas phase. The resulting polymer films were smooth and pinhole free. The electrical conductivities of the polymer films varied from 10−12 to 10−7 S cm−1 depending upon which cyano‐containing monomer was used. The Al/polymer film/ITO (indium‐tin oxide) sandwich cells made from the films demonstrated a photovoltaic effect, and some of them showed good rectifying behavior. Infrared spectroscopy (IR) and ultraviolet spectroscopy (UV) were utilized to characterize the structure of the product polymers. The effects of the original structure in the starting monomers on the structure of the resulting polymers are investigated. The influence of incident light intensity on the photovoltaic characteristics was also investigated.
Radical polymerization of styrene initiated by styrene–arsenic sulfide complex
Authors: Shukla Prerna , Srivastava A. K. 
Published: April 2003

AbstractStyrene forms a complex with arsenic sulfide which in DMF at 85°C initiates radical polymerization yielding high molecular weight polymer. The order of reaction, with respect to initiator and monomer, is 0.5 ± 0.02 and unity, respectively. The energy of activation for the system computed as 96 kJ mol−1 and the polymerization is retarded by hydroquinone. A possible mechanism for reaction has also been proposed.
Investigation of the ceriumIV oxidation of poly(vinyl alcohol)
Authors: Storey Robson F. , Goff Leslie J. 
Published: April 2003

AbstractInitiation of ceric ion‐induced grafting from poly(vinyl alcohol) (PVOH) was studied by examining the formation and lifetime of colored complexes between ceriumIV and (1) a commercial PVOH, (2) a diol‐free PVOH, and (3) several model 1,2‐diols. UV/visible spectroscopy was employed using a wavelength of 520 nm. Results showed that the 1,2‐diols, which are an inherent defect in PVOH, are the sites most reactive toward ceric ion. The observed rate constant for the reaction was found to increase with decreasing [CeIV] until the maximum rate was reached at which time reaction took place exclusively with 1,2‐diols. The activation energy for oxidation of commercial PVOH at the maximum rate was 15.4 kcal/mol while that for diol‐free PVOH was 22.4 kcal/mol. The 1,2‐diols of PVOH displayed a high equilibrium constant for complexation with ceric ion, compared to the model 2,3‐butanediol. It was suggested that the PVOH chain segments bring about crowding of the diol group, and this leads to a higher equilibrium constant for complexation. The lowest energy conformation of a PVOH chain segment containing a 1,2‐diol linkage was calculated using the CHEMLAB‐II molecular design program, and the 1,2‐diol was predicted to be at the center of a sharp bend in the chain brought about by its presence.
Preparation and properties of some water‐soluble, comb‐shaped, amphiphilic polymers
Authors: Wesslén Bengt , Wesslén K. Bodil 
Published: April 2003

AbstractWater‐soluble comb‐shaped polymers were prepared through grafting of poly(ethylene glycol) monomethyl ethers (MPEG) onto acrylic and methacrylic ester copolymers by transesterification reactions. The grafting was alkali‐catalyzed, and performed in refluxing toluene solution or in melt at 155°C. The grafting efficiency was found to be on the order of 1 graft/10 monomer units. Epoxy groups in glycidyl methacrylate copolymers were also utilized for grafting. The crude graft copolymers were purified through chromatography and characterized by NMR and IR spectroscopy. Polymers prepared from MPEG 2000 were crystalline with melting points 10–15°C lower than the MPEG used. All polymers were shown to be surface active with CMC on the order of 1.5 g/L, and surface tensions of 38–45 dyn/cm. When used as emulsifiers the graft copolymers containing bulky lipophilic ester groups (2‐ethylhexyl t‐butyl) gave oil‐in‐water (o/w) and water‐in‐oil (w/o) emulsions from xylene/water with higher stability than those containing straight chain ester groups (methyl nbutyl n‐docecyl). The most stable emulsions were obtained by dissolving the polymers in the organic phase.
Impact of degree of phosphorylation on intrinsic and thermal properties of poly(styrenephosphonate diethyl ester)s
Authors: Sun Jing , Cabasso Israel 
Published: April 2003

AbstractThe intrinsic and thermal characteristics of poly(styrenephosphonate diethyl ester)s (PSP) are described. The properties of the polymer prepared by two synthetic procedures, phosphorylation of monodispersed polystyrene and polymerization of vinylbenzenephosphonate ester, are compared with chloromethylated polystyrene and with each other. Empirical formulas are presented for the relationships between the degree of polymerization, degree of phosphorylation, molecular weight, and intrinsic viscosity (in methanol and toluene). Thermal analysis reveals a sharp drop in Tg with an increase in degree of phosphorylation; Tg of the fully phosphorylated polystyrene is in the range of 9–30°C. The Tg ΔCp values show significant decrease with augmentation in the degree of phosphorylation, yielding a value of 14 cal g−1 for the fully phosphorylated polymer, compared with ∼ 29 cal g−1 for the parent polymer. The PSP is shown to have substantial capacity for dissolving heavy metal salts, such as UO2(NO3)2, causing significant elevation in the Tg.