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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    International ophthalmology 1 (1979), S. 109-122 
    ISSN: 1573-2630
    Keywords: Photocoagulation ; Non-linear effects ; Physics ; Morphology ; Nd glass Q-switched laser ; Scanning electron microscopy ; Chamber angle ; Monkey
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Working at a power density above optical breakdown threshold, irradiation effects upon the angle of the anterior chamber of the Macaca speciosa monkey by a Nd glass Q-switched laser, have been analysed with scanning electron microscopy. Two different damage effects can be identified: openings of Schlemm's canal and the creation of a cyclodialysis, that is opening the uveoscleral outflow routes; the latter may be a more effective one than the former. Also a third mechanism, namely a structural alteration of the trabecular meshwork, at the molecular level by laser action, has been inferred. The physical effects leading to optically induced mechanical damage are discussed. Applicability of such effects upon the morphological findings described here, is limited and to a greater part speculative. A better definition of the physical parameters, required for optimal therapeutical damage effects in the treatment of the wide angle glaucoma may be obtained by trial and error methods, which are guided by the results of electron microscopical analyses of samples obtained from in vivo and in vitro experiments.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1-7 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of thermal polymerization of methyl methacrylate initiated by the redox system Mn(III)-glycerol was studied in aqueous sulfuric acid in the temperature range of 30-40°C, and the rates of polymerization, Rp, and Mn3+ disappearance, etc., were measured. The effect of certain water-miscible organic solvents and certain cationic and anionic surfactants on the rates of polymerization has been investigated. A mechanism involving the formation of a complex between Mn3+ and glycerol whose decomposition yields the initiating free radical with the polymerization being terminated by the metal ion has been suggested.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 9-18 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Eleven N-substituted carbazoles (CZ) with terminal vinyl groups were synthesized by five sequences of reaction: N-(p-vinylbenzyl)- and N-β-(vinyloxyethyl)CZ by N-alkylations of potassium CZ with corresponding chlorides; N-(β-acryloyloxyethyl)CZ by the esterification of N-(β-hydroxyethyl)CZ with acryloyl chloride; N-acrylamido-or methacryl-amido-methyl CZ from N-hydroxymethyl CZ and acryl- or methacrylamide; N-(3-acryloyl- or methacryloyl-oxy-2-hydroxypropyl)CZ and N-[3-(p- or m-vinylanilino)-2-hydroxypropyl] CZ from N-(2,3-epoxypropyl)CZ and acrylic or methacrylic acid and p- or m-vinylaniline, respectively; and 2-[β-(N-carbazyl)propionyloxy]ethyl acrylate or methacrylate by the Michael addition of CZ to 2-hydroxyethyl acrylate or methacrylate, followed by esterifications. The vinyl polymers with pendant carbazyl groups more or less distant from the polymer backbones, prepared by conventional radical or cationic polymerization procedures, indicated charge-transfer spectra with 2,4,7-trinitrofluorenone (TNF) in tetrahydrofuran (THF) solutions that are spread over most of the visible range.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 69-80 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of tetrahydrofuran (THF) in CH3NO2 solvent was initiated with 1,3-dioxolan-2-ylium cations with AsF6- and SbF6- anions, as well as with esters of FSO3H and CF3SO3H acids. Polymerization shows in this solvent a living feature: values of kp (determined directly from the semilogarithmic kinetic plots) were the same for all of the listed above initiators; thus kp is the same for AsF6-, CF3SO3-, FSO3-, and SbF6- anions. The identity of the kp values for complex and noncomplex (ester-forming) anions comes from the fact that in CH3NO2 solvent equilibrium between macroesters and macroion pairs is shifted almost completely (Ke = 33.0 at 25°C and |THF|0 = 7.0M) to the macroions side. Dissociation constants of the polytetrahydrofuranium ion pairs (CF3SO3- and SbF6- anions) were measured (e.g., KD = 2 × 10-3 M at 25°C and |THF|0 = 7.0M; i.e., at D = 22.8, ΔHD = -3.8 ± 6 kcal mole; ΔSD = -25 ± 2 eu). On the basis of the known values of KD, and therefore dissociation degrees α, rate constants of propagation on the free and paired THF cations (kp+ and k+±) were determined for a large range of degrees of dissociation (α from 0.15 to 0.52). The rate constants kp+ and kp± were found to be the same within an experimental error of measurements (± 15% of the value of kp). Apparently, the polytetrahydrofuranium cations are highly solvated or even separated from their anions by molecules of THF itself. At these conditions the reactivities of the solvated “free” and solvated (or separated) paired cations became undistinguishable.
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  • 5
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(N-aryl maleimide)s of characteristic structures have been synthesized and some of their physical properties studied. These include N-(2-fluoro phenyl), N-(3-fluoro phenyl), N-(4-fluoro phenyl), N-(2,4-difluoro phenyl), N-(2,5-difluoro phenyl), N-(2,3,5,6-tetrafluoro phenyl), and N-(pentafluoro phenyl). The polymerization of N-(fluoro phenyl) maleimides by free-radical initiation in bulk or in solution and by anionic catalyst have been studied to compare the characteristics of polymerization by γ-ray irradiation with that by free-radical initiation. The polymers were characterized by elemental analysis, intrinsic viscosity, spectroscopy (IR and NMR), programmed thermogravimetric analysis, and x-ray diffraction. Spectra of polymers prepared by radiation and anionic polymerization were nearly identical with those of polymers prepared by free-radical polymerization initiated by AIBN in bulk or in solution and by the self-initiated thermal polymerization. A variety of reaction conditions were tried, but all attempts to change the molecular structure of the polymers were unsuccessful. Rates of thermal degradation for poly[N-(fluoro phenyl) maleimide]s have been analyzed by using a multiple-heating-rate procedure. Overall activation energy, order of reaction, and frequency factor have been evaluated. On the basis of the comparison between the overall activation energy of the thermal degradation of poly[N-(fluoro phenyl) maleimide]s and NMR spectra of their corresponding monomers, it can be concluded that the 1H shifts due to ethylenic protons are so characteristic in sign and magnitude as to be useful in thermal stability elucidation. Some qualitative explanations were given on the stability of these polymers as affected by the type and size of the substituent. The x-ray diffractograms of all samples show two rather broad peaks indicative of noncrystalline structures. The location of the peaks does not depend upon preparation conditions and temperature. Poly(N-maleimide)s of fluoroanilines have not been hitherto described.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 97-109 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The triethylamine-initiated polymerization of glycine-NCA [N-carboxylic acid anhydrides (oxazolidine-2,5-diones)], L-alanine-NCA, and sarcosine-NCA, as well as the pyridine-initiated polymerization of sarcosine-NCA, were carried out in the presence of potential cocatalysts. The 11 electrophilic reagents tested in this work can be divided into two classes: N-acyllactams and similar compounds, which are less reactive than the monomers and have no influence on the polymerization; and isocyanates and N-acyl-NCAs or -NTAs [N-thiocarboxylic acid anhydrides (thiazolldine-2,5-diones)], which are more electrophilic than the monomers and behave as cocatalysts in the case of glycine-NCA and alanine-NCA, since their base-initiated polymerization proceeds via the attack of NCA anions on the electrophilic N-acyl NCA chain and (“activated monomer mechanism”). In the case of sarcosine-NCA, however, the propagation involves a nucleophilic chain end (“carbamate mechanism”) and the strong electrophilic reagents behave as inhibitors.
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  • 7
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The size, distribution, and number of PTFE particles formed by radiation-induced emulsifier-free polymerization were measured by electron microscope and automatic particle analyzer (centrifugation method). From the electron micrographs we found that the particles are formed within 5 min. The change in the number of polymer particles (np) with reaction time (t) depends on the relative concentration of growing polymer chains to stabilizing species produced by the radiolysis of water and monomer; that is, it was governed by TFE pressure/dose rate ratio and classified into three cases: case I, dnp/dt = 0 (e.g., at 3 × 104 rad/hr and 20 kg/cm2); case II, dnp/dt 〈 0 (e.g., at dose rate below 1.9 × 104 rad/hr and 20 kg/cm2); case III, dnp/dt 〉 0 (e.g., at 3 × 104 rad/hr and 2 kg/cm2). The polymer molecular weight above 106 is almost independent of the particle size. The polymerization loci are mainly on the surface of polymer particles dispersed in the aqueous phase in cases I and II except in the initial stage. In case III new particles are formed successively during polymerization. Therefore the polymerization loci are mainly in the aqueous phase. Especially in case I, we concluded that after the generation of particles the propagation proceeds mainly on the surface of polymer particles like the core shell model proposed by Granico and Williams.
    Additional Material: 10 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 139-145 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of poly(vinyl chloride) (PVC) with superoxide anion was carried out in tetrahydrofuran (THF) at 40°C in a nitrogen atmosphere. Remarkable changes in infrared (IR) spectra of the samples treated with superoxide anion were observed in the following regions: ca. 3300, 1680, 1620, and 765 cm-1, which suggested the formation of hydroxyl groups, α,β-unsaturated ketone groups, and ethylenic structures. Ultraviolet-visible spectra also showed the formation of polyene structures. The content of chlorine in the polymer decreased and that of oxygen increased with reaction time. The reaction mechanism was discussed on the basis of these results.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 147-154 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to assess the effect of the methylol group at the 4-position of 1,3-dioxolane on polymerization, the photopolymerization of 2-vinyl-4-hydroxymethyl-1,3-dioxolane (VHDO) was carried out in benzene at 40°C. The reaction scheme of VHDO was considered to be the same as that of 2-vinyl-1,3-dioxolane (VDO). The rate of polymerization and the molecular weight of polymer were small because of the degradative chain transfer by allylidene group. Moreover, the rate of polymerization of VHDO was greater than that of VDO, whereas the molecular weight of polymer of VHDO was less than that of VDO.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 155-162 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To determine the content of trans-gauche-trans (TGT) conformation in poly(ethylene glycol) (PEG) 1H-NMR spectra were measured with tris(1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-1,4,6-octanedinato)europium(III) [Eu(fod)3] as a shift reagent. As a result the peaks assigned to the ethylene protons in the polymeric segments separated from those assigned to four ethylene protons as the “near-end” groups, and the singlet peak in the former at the lowest field was assigned to the TGT conformation of the COCCOC sequence. It was confirmed that the conformation of the polymeric segments in PEG complexed with Eu(fod)3 remained unchanged with benzene-d6 content as the solvent. The concentration of TGT conformation increased with the number-average molecular weight (Mn): it increased rapidly until about 70% at Mn = 1500.
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  • 11
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 129-138 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Simultaneous formation of hydrofluoric acid (HF) in the radiation-induced polymerization of tetrafluoroethylene (TFE) was investigated. HF concentration in PTFE latex was determined mainly by conductometric titration with 0.01 and 0.001N NaOH. The amount of HF formed is almost independent of agitation speed and the amount of n-hexadecane added and is maximal at ca. 70°C corresponding to the rate of polymerization.The rate of HF formation increases with the initial pressure of TFE monomer and dose rate and decreases with polymerization or TFE consumption. This fact suggests that HF is formed mainly by TFE reactions and not by the degradation of PTFE.The mechanism of HF formation in this reaction system in the absence of oxygen is shown in the following two schemes: scheme I is the reaction of TFE with primary radicals (OH·, H·, eaq-) from the radiolysis of water; scheme II is the reaction of water with the species from the radiolysis of TFE. On the assumption that HF is formed only according to scheme I, the G value of HF formation G(HF)calc can be calculated as 11.25. All observed G values G(HF)obs are larger than G(HF)calc. When the polymerization is carried out at 20 kg/cm2 under various dose rates, G(HF)obs increases with the dose rate. When the polymerization is carried out at 3.0 × 104 rad/hr under various pressures, G(HF)obs decreases with the decrease in pressure from 20 to 2 kg/cm2 and is fairly close to G(HG)calc at 2 kg/cm2. This indicates that HF formation is due mainly to scheme II at high pressure (in the presence of enough TFE) and to scheme I as the pressure is lowered.
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 163-172 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polybenzimidazoles (PBI) with p-phenylene and/or cis-vinylene groups in the backbone were prepared from terephthalic acid (T), maleic acid (M), and 3,3′ diamino-benzidine tetrahydrochloride dihydrate (DAB) in poly(phosphoric acid) (PPA). Five polymer samples were prepared by varying the M:T molar ratios in the following order: 1:0, 1:1, 2:1, 1:2, and 1:4. The polymers were characterized by intrinsic viscosity, density, electronic fluorescence, and IR spectra. The effect of composition on the solubility of the polymers in various organic solvents was also investigated. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in air and polybenzimidazoles (PBI) with cis-vinylene groups were found to be less stable.
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 193-202 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potentiometric titrations in water of high-molecular-weight partly hydrolyzed polyacrylamides were analyzed by the Lifson - Katchalsky rodlike model. A fair concordance was found between theory and experimental curves with pK0 of acid functions of about 4.75 when 0 〈 τ 〈 0.49. Two methods were derived to calculate the parameter n of the extended Henderson-Hasselbach equation by using a series expansion of pKa vs. α, not yet reported in the literature. A new equation for n was established and comparison between two sets of values of n, obtained by using the theoretical ΔpK curves and series expansion is discussed.
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 271-275 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 15
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 255-266 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alternating polyampholytes (MA-VA) containing two acidic groups and one basic group were prepared by the copolymerization of maleic anhydride (M1) and N-vinylsuccinimide (M2) at 60°C with AIBN as the initiator, followed by acid hydrolysis with 1N hydrochloric acid at 140°C for 24 hr. The monomer reactivity ratios r1 and r2 are 0.025 and 0.06, respectively. The structure of polymers was discussed on the basis of the data of their elementary, infrared (IR), and thermal analyses and the binding ability of heavy metal ion. Polyampholytes were soluble in strong acidic and basic media but were precipitated in the pH range 3-4. An isoelectric point at pH 3 was determined by potentiometric titration and the turbidimetric method. By thermal treatment above 205°C the polyampholyte turned quantitatively into a cyclized lactam. This suggests that the polyampholyte MA-VA has an intramolecular hydrogen bond between the amino and γ-carboxyl groups. The binding of Cu2+ and Hg2+ by the polyelectrolyte was evaluated by equilibrium dialysis.
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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 277-279 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 287-291 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 18
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 281-286 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 293-297 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 20
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 313-318 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new, easily processed, organic semiconductor was prepared from poly(vinyl alcohol) (PVA). The Cu2+ chelate of PVA exhibited excellent surface resistivity around 103 Ω cm-2 when modified with iodine. Favorable conditions for preparing the chelate effective for the conduction were investigated. The resistivity was significantly affected by the amounts of cupric salts and iodine, satisfactory results being given by more than 15 wt% of cupric salts and about 4 wt% of iodine. Effects of molecular weight of PVA and the chelate structure were also studied.
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  • 21
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    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 301-312 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Behavior of the free radical copolymerization of N-β-methacryloyloxyethyl derivatives of adenine with that of thymine was studied in chloroform solution, taking account of the specific base-base interaction of these monomers. Hydrogen bonding interaction between such monomers was observed by NMR spectroscopy. The acceleration of copolymerization was found to be greater either at lower monomer concentration or at lower polymerization temperature. When N-β-methacryloyloxyethylcarbazole was used as a comonomer, the rate of copolymerization showed a similar trend as in the case of usual free radical copolymerizations. From r1 and r2 values obtained, the copolymerization was found to be alternating, particularly in the case of copolymerization between monomers having complementary nucleic acid bases. The results suggest that the hydrogen bonding interaction between adenine and thymine plays a role in the propagation step.
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  • 22
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 331-349 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Methyl-3-methylenecyclobutene (MMCB) and 1,2-dimethylenecyclobutane (DMCB) copolymerized readily with isobutene with aluminum chloride as initiator in methyl chloride solution at temperatures from -95 to -78°C. No polymers were obtained with methylenecyclobutene (MCB) under similar conditions. The copolymerization of MMCB with isobutene took place through a 1,5-addition reaction while that of DMCB through both 1,2- and 1,4-addition reactions. Large amounts of gel were present in the copolymers obtained from DMCB if the reaction was carried to high conversion. The commonly observed effects of dienes (i.e., rate retardation and molecular weight depression) on cationic copolymerization reactions were observed but to a much higher degree with these small ring dienes. The thermal crosslinking behavior of the resulting copolymers was investigated. In conjunction with the copolymerization studies, homopolymers of MMCB, DMCB, and 3,3-dimethyl-1-isopropylidene-2-methylenecyclobutane (IMCB) were prepared and their chemical structures examined.
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  • 23
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 377-384 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,2,4-Trimethyl-3-on-1-pentyl methacrylate (TMPM) was first synthesized from the condensation reaction of 2,2,4-trimethyl-1-pentanol-3-on with methacrylic acid. Second, the polymerization of TMPM and the copolymerization of TMPM with styrene (St) were carried out in benzene at 60°C, using 2,2′-azobisisobutyronitrile (AIBN) as an initiator. As the result of kinetic investigation, the rate of polymerization (Rp) could be expressed by: Rp = k[AIBN]0.5 [TMPM]1.0. Kinetic constants of polymerization of TMPM were obtained as follows: kp/kt1/2 = 0.27 dm3/2 mole-1/2 sec-1/2, 2fkd = 1.23 × 10-5 sec-1, f = 0.73, Cm = 2.6 × 10-5, Cs = 1.1 × 10-5. From the results the reactivity of TMPM was found to be larger than that of methyl methacrylate. The overall activation energy was calculated to be 110 kJ mole-1. The following monomer reactivity ratios and Q, e values were obtained: TMPM(M1) - St(M2): r1 = 1.50, r2 = 0.14, Q1 = 2.63, E1 = 0.45.
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  • 24
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 393-404 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of dose rate on the rate of polymerization and molecular weight distribution of radiation-induced polymerization of styrene adsorbed on silica gel was studied in a wide dose rate range of 4.4 × 104 to 3 × 108 rad/hr by γ rays of 60Co and electron beams with a Cockcroft-Walton-type accelerator. Dose rate dependence on the initial rate of polymerization was about 1 below 3 × 107 rad/hr, and it decreased gradually at high dose rates. Throughout the dose rate range, graft polymerizations and homopolymerizations by cationic and radical mechanisms proceeded simultaneously. Dose rate dependence of the cationic polymerization was 1 below 3 × 107 rad/hr, while dose rate dependence of the radical polymerization was 0.65 below 3 × 107 rad/hr. At high dose rates, molecular weight and fraction of graft polymer decreased, and fraction of cationic polymerization increased. A very high-molecular-weight graft polymer was formed above 4.4 × 105 rad/hr at the initial stage of the polymerization. The dose rate dependence of this polymerization was larger than 1 and decreased with increase in dose rate. The polymerization seems to be related to an excitation of monomer or growing chain.
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  • 25
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 435-439 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The color stability of high nitrile polymers is increased by dienophilic stabilizers; however, the stabilization reaction is greatly affected by the presence of residual metal ions. This effect is correlated with electronegativity considerations of the metal ion. Metal ions affect the stability of the polymer whether they are used to coagulate the latex or postadded to the dry resin. Coagulation with group IIA metal ions results in polymer capable of stabilization by dienophiles. The mechanisms of stabilization and degradation in the presence of residual metals are discussed.
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  • 26
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 455-464 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the intermediates in unterminated polymerization reactions were studied. It was found that in a first-order initiation (A) all intermediates accumulate monotonically. In a second-order initiation (B) the first intermediates pass through a maximum, whereas the later ones strictly accumulate. An initiator-started polymerization can follow course A or course B, depending on the initial ratio of the concentrations of the initiator and monomer.
    Additional Material: 5 Ill.
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  • 27
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photooxidative degradation of cellulose resulted in decreases of degree of polymerization (DP) and α-cellulose content, concurrently producing chromophoric groups; namely, carbonyl, carboxyl, and hydroperoxide groups within the polymer. Electron spin resonance (ESR) studies revealed that cellulosic carbon free radicals readily reacted with oxygen molecules at 143-160 K to produce peroxy radicals, whereas cellulosic oxygen free radicals were inert toward oxygen molecules throughout the photooxygenation reactions. At 77 K it is feasible that only photoexcited oxygen molecules reacted with cellulosic carbon free radicals to produce peroxide radicals. These radicals were themselves stabilized at 273 K by abstraction of hydrogen atoms from cellulose to produce polymer hydroperoxides. Simultaneously, new radical sites, which exhibited three-line ESR spectra, were generated in cellulose.
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  • 28
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 613-616 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 29
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 603-612 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aqueous polymerization of methyl methacrylate with sodium bisulfite as initiator was catalyzed by PbO—SiO2, PbO (70 mole %)—SiO2 (30 mole %) with a particle size 〈 200 mesh had the highest catalytic effect. The average molecular weight obtained in the presence of amorphous PbO—SiO2 glass was higher than that obtained in the presence of crystalline PbO - SiO2 glass powder. In this system mild shaking increased the rate of polymerization. Silicon dioxide catalyzed the rate of polymerization to a higher extent than PbO, which had a slightly higher catalytic effect than lead silicate powder. The average molecular weight formed in the presence of PbO was higher than that formed in the presence of lead silicate, which in turn was higher than that formed in the presence of silicon dioxide. Increasing the initiator concentration decreased the average molecular weight. Mild shaking decreased the average molecular weight obtained when polymerization was carried out in air but increased it in a nitrogen atmosphere. Methanol decreased the conversion percentage of monomer to polymer and the average molecular weight due to its transfer reaction.
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  • 30
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 619-626 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reaction of equimolar quantities of isophthalonitrile and o-carborane has been shown to produce an adduct oligomer of isophthalonitrile. The structure was determined to involve condensation of three to five isophthalonitrile molecules to form a triazine-type system. This type of bonding gave rise to a trimer and pentamer. Further, the reaction was a homogeneous liquid phase reaction in which o-carborane is involved in a catalytic manner in the oligomerization. The overall reaction has first-order kinetics with an activation energy of 32.2 kcal/mole.
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  • 31
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 627-638 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sample charging phenomena arising in the ESCA experiment have been investigated for gold and polymer films of known thickness ranging from 5 Å to 20 μ deposited on gold either insulated from or in electrical contact with the spectrometer. Charging induced by a monochromatic x-ray source is typically an order of magnitude greater than that induced by a nonmonochromatized source and exhibits a marked time dependence. A novel source of secondary electrons which employs a low-power, low-pressure mercury lamp external to the spectrometer source chamber as an alternative to an electron flood gun is described, and the charging and biasing characteristics of polymer films as a function of film thickness are discussed and demonstrated to provide an extra informational dimension for the study of polymeric materials.
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  • 32
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: SAXS measurements on dilute solutions of polyisobutene in n-hexane (Mν = 25,600-3.55 × 106, c 〈 53 g/liter) were carried out by combining conventional slit collimation with the new cone collimation technique. With a fractionated sample (Mν = 25,600; U 〈 0.2) the radius of gyration (R = 48 Å), the cross-sectional radius of gyration (Rq = 3.9 Å), the molecular weight per unit length (M/L = 22.8 Å-1), and the Porod persistence length (a* = 8.1 Å) are found. The persistence length appears to be dependent on the molecular weight. The partial specific volume ν of polyisobutene in n-hexane also depends on the molecular weight according to ν = 1.025 + 105/Mν (cm3/g).
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  • 33
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 649-658 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electric properties of polymer composites with highly conductive 7,7,8,8-tetracyanoquinodimethan (TCNQ) salts such as quinolinium-TCNQ complex salt (), acridinium-TCNQ complex salt (), and N-methylacridinium-TCNQ complex salt () were studied. Polyacrylonitrile (PAN), poly(N-vinylcarbazole) (PVK), and poly(4-vinylpyridine), (P4VP), etc., were chosen as matrix polymers. The resistivity (ρ) of the was 0.37 Ω cm at the content of 20 wt % in the film. When the content of was increased up to 40 wt%, a phase separation of the needle crystals was observed and the ρ value increased. When was dispersed into PAN or PVK, the separation was also observed and the samples showed low conductivity. The uniform films were obtained in the and systems, but the values of ρ were high because of the degradation of the TCNQ salts. Uniform films with the naked eye were obtained in the and systems, and the values of Ω were 0.37, 1.05, and 3.40 Ω cm, respectively. was stable even when dispersed into P4VP. The properties of the composites were influenced by the combination of the TCNQ salts and the polymers. The uniformity and the stability of the composites were necessary to obtain the high conductive composites.
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  • 34
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 659-672 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of ionization (α) and added salts (NaCl, CaCl2, MgCl2) on the dimensions of commercially available high-molecular-weight polyacrylamides (Mw ≃ 4 × 106), hydrolyzed at various extents (0.04 〈 τ 〈 0.49) and which have been characterized, was investigated by viscosity and light-scattering measurements performed at 25°C. The data point with evidence to the strong dependence of the chain dimensions on the charge density (ατ) and the effect of the nature and concentration of added salts. From a practical point of view it is shown that there is no advantage to using too highly hydrolyzed samples (τ 〉 0.45) in media containing large amounts of salts that lead to precipitation of polymers, especially in the presence of divalent ions.
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  • 35
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 683-692 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crosslinking mechanism and kinetics of low-molecular-weight polybutadiene, its mixtures with maleic anhydride, and the products of its grafting with maleic anhydride and styrene, using dicumyl peroxide (DCP) as an initiator, were studied. It was shown that for all systems crosslinking is a radical polymerization of the double bonds. Modification of polybutadiene changes only the kinetic parameters of the crosslinking reaction and causes mainly a decrease of the termination step velocity. From DSC data the crosslinking reaction order, activation energy, and reaction heats were calculated.
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  • 36
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 673-681 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of n-butyl vinyl ether polymerization by chromyl chloride is first order in [catalyst] and second order in [monomer]. Added H2O (after a certain concentration) and HCl increase the rate, thiophene retards the rate, while pyridine inhibits the rate. DP is independent of [chromyl chloride] and increases with increasing [monomer] up to 1M, thereafter becoming independent of it. Both rate and DP increase over the range 10-32°C and decrease at higher temperatures.
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  • 37
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 703-713 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyimides with different proportions of m-phenylene and p-phenylene (or p,p′-biphenylene) were prepared by polymerizing different molar ratios of m-phenylene diamine and p-phenylene diamine (or p,p′-diaminobiphenyl) with pyromellitic dianhydride in dimethylformamide at 0°C. Chemical cyclodehydration of polyamic acids resulted in the corresponding polyimides. Polymers were characterized by infrared (IR), viscosity, and density measurements. Viscosity and density of polymers decreased with an increase on m-phenylene groups in the backbone. The thermal and thermooxidative stabilities were investigated by dynamic thermogravimetry. Stability decreased when m-phenylene groups were introduced in the backbone.
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  • 38
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 693-701 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermoelastic (stress-temperature) measurements in elongation have been carried out on polyurethane elastomers obtained from poly(ethylene adipate), poly(ethylene maleate), poly(ethylene glycol), and 4,4′-diphenylmethane diisocyanate. The elastomers were crosslinked by an excess of diisocynate and some of them were additionally crosslinked by dicumyl peroxide. Values of the temperature coefficient d ln r02/dT of the unperturbed dimensions of the network chains and the fraction fe/f of the stress, which is due to energetic effects, were calculated from measurements of unswollen samples and samples swollen in benzene to a constant volume fraction ν2 of about 0.6. The coefficient d ln r02/dT and the ratio fe/f for unswollen samples were positive but dependent on the extension ratio α and crosslinking density. The fe/f ratio displayed a tendency to decrease with increasing α and this decrease was smaller for elastomers of higher crosslinking density. Additional crosslinking due to dicumyl peroxide reduced the dependence of fe/f on α. Swollen samples had lower positive values of fe/f; which were somewhat independent of α and crosslinking density. Departures from the molecular theories of rubberlike elasticity are explained by intermolecular effects, which, in general, are influenced by crosslinking.
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  • 39
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 715-729 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied the rose bengal-sensitized photooxygenation of cis- and trans-polyisoprene model compounds that contain one unit in methanolic solution, characterized the resulting monohydroperoxides, and determined their yield. We have also demonstrated the possibility of a second addition of singlet oxygen on the same unit and have undertaken a kinetic study to determine the rate constants of all the reactions of 4-methyl-4-octene.
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  • 40
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of Et2SO4, (S)-1-(N-phenyl-carbamoyl)-2-methylaziridine gave an oligomer with a structure of [CH2—CHCH3—N(CONHPh)]n. The oligomer has optically active isotactic configuration and narrow molecular weight distribution (DP ca. 8). The net polymerization behavior of the monomer and chemical property, such as absorptivity of Et2SO4, of the oligomer are analogous to the case of 1-(N-phenyl-carbamoyl)-aziridine. The ring opening occurs with retention of the configuration at the asymmetric carbon atom and the oligomer can be crystallized at around 90°C.
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  • 41
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 747-757 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In due consideration of the specific base-base interaction that exists between nucleic acid molecules, the free radical polymerization of N-β-methacryloyloxyethyl derivatives of adenine, thymine, and theophylline initiated by azobisisobutyronitrile (AIBN) was studied in the presence of N-β-methacryloyloxyethyl-type polymers which have complementary nucleic acid bases as template polymers. The rate of polymerization of N-β-methacryloyloxyethyladenine was accelerated when poly(N-β-methacryloyloxyethyluracil) or -thymine was present in the polymerization system. The effect of the stereoregularity of the template polymers, as well as polymerization temperature and the sort of solvents used on the rate of polymerization, was studied and discussed in some detail. The results suggest that the interaction between complementary bases plays a role in template polymerization behavior.
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  • 42
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 759-768 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-induced copolymerization of tetrafluoroethylene (A) and styrene (B) was studied in bulk and in perfluorotoluene at 22°C at autogenous pressure and 260 and 510 MPa. The reactivity ratio for addition to A-ended radicals, rA, is effectively zero at the two lower pressures and is in the range 0.002-0.008 at 510 MPa. The other reactivity ratio, rB, is 6 at autogenous pressure and also at 260 and 510 MPa if the A content of the charge is less than 50%. If the A content is greater than 95%, rB appears to be 100 at pressures of 260 and 510 MPa. The apparent variation in rB cannot be explained by invoking a penultimate unit effect for B-ended radicals. Polymerization rates scatter somewhat, but all rates are quite small when the A content of the charge is in the range 95-99.8%. Polymers containing as much as 66% A appear to be inherently benzene soluble but frequently contain some gel because of radiation-induced crosslinking after their formation. No very high polymers were formed that contained more than a few percent A, even at high pressure. Features that complicated the study were immiscibility of the liquid monomers, extreme variation of the monomer - copolymer compatibility with charge composition, and freezing of B at high pressure.
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  • 43
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 769-775 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aminolysis of benzoic mesitoic anhydride was studied in a model system to select the reaction site by steric effect and was found to occur exclusively at the carbonyl group of the benzoic acid. Solution polycondensation of new linear bisanhydrides, terephthalic bis(mesitoic anhydride) and adipic bis(mesitoic anhydride), with aromatic diamines in polar aprotic solvents that contained lithium chloride at room temperature, afforded polyamides with high molecular weight. The interfacial polycondensation in a dichloromethane-water system also successfully yielded polyamides from aliphatic diamines.
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  • 44
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 777-782 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photocrosslinking has been observed in a number of polymers derived by chemical modification of poly(vinylbenzyl chloride). Included are polymers bearing pendant benzophenone, stilbazolium, fluorenone, carbazole, and sulfonylazido moieties. The synthesis and properties of these polymers are described.
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  • 45
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 783-787 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Catalytic actions of various additives were studied in the polycondensation of di(4-nitrophenyl) isophthalate with bis(4-aminophenyl) ether in N-methyl-2-pyrrolidone, and 1-hydroxybenzotriazole (HOBt) was found to be a highly effective catalyst that yielded high-molecular-weight polyamide. In addition to the polycondensation of the 4-nitrophenyl ester, the polymerization of negatively substituted phenyl esters like di(2,4,5-trichlorophenyl) isophthalate was also accelerated by HOBt. For the HOBt-catalyzed aminolysis of esters a bifunctional concerted mechanism that involves an eight-membered transition state was proposed.
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  • 46
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 797-806 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the basis of the simultaneously measured free radical generation and HCl evolution a mechanism accounting for the effect of the oxygen on the degradation of poly(vinyl chloride) (PVC) is proposed. The mechanism is based on the reaction of oxygen with radicals generated in PVC to form unstable peroxy radicals. In addition, it is proposed that oxygen reacts directly with conjugated polyenes to form peroxy linkage.
    Additional Material: 6 Ill.
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  • 47
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 789-796 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To enhance its solubility in common solvents poly(γ-methyl-L-glutamate) (PMG) was transesterificated with ethylene chlorohydrin, ethylene cyanohydrin, and β,β,β-trichloroethanol, respectively. The aminolyses of the resulting polymers proceeded easily in pendant ester groups to give the corresponding amides in reasonable yields without main chain fission. By these procedures the incorporation of functional groups such as azide, amino acid, and thiol into PMG is successfully performed.
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  • 48
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 807-813 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equilibrium constants of the coordination reaction of chlorodimethylformamide·cobaloxime with 4-vinylpyridine-styrene copolymers (PPS) were determined. The constants for PPS, which contain 20-50% 4-vinylpyridine (4VP) unit, measured about 1.3 × 105 liter/mole larger than those in the pyridine system (6.8 × 104 liter/mole). When the polymer ligand is 4VP homopolymer or contains less than 20% 4VP unit, K values are lower. The rate constants (kf) of the coordination reactions of the cobaloxime with polymer ligands were also measured in dimethylformamide (DMF) and benzene. In DMF kf decreased with an increase in 4VP unit content of the polymer ligand; in benzene it was increased by the 4VP fraction. These results can be explained by the variation in conformation of the polymer chain in each solvent. The effect of the polymer chain on complexation was discussed on the basis of the kinetic data.
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  • 49
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 821-833 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The neighboring effect of sodium carboxylate groups on the saponification of diallyl phthalate prepolymer was investigated in detail in dioxane solutions that contained various amounts of water at 50°C by using different types of model compound; this procedure is also compared with the neighboring effect of hydroxyl groups.
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  • 50
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 815-820 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photopolymerization of cyclohexene oxide in the presence of electron acceptors was studied in a bulk system (in liquid as well as in solid states). The polymerization was proved to proceed by a cationic mechanism in both states by the effect of inhibitors. In a liquid phase the light intensity dependence of the rate of polymerization and the molecular weight distribution showed a contribution of a free ionic polymerization. Any discontinuous phenomenon in the rate as well as in the molecular weight was not discerned between liquid(above -36°C) and plastic crystal (between -36 and -81°C) phases. A quantum yield of monomer consumption as high as 8 × 103 was observed in the plastic crystal phase. Below -81°C in the normal crystal phase the rate as well as the molecular weight was remarkably suppressed.
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  • 51
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 835-841 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Selective formation of biscarbamates from diphenyl carbonate (DPC) and diamines and the preparation of polyurethanes from the carbamates and diols under mild conditions were studied. The reaction of DPC and diamines was significantly affected by catalysts, biscarbamates being exclusively prepared in high yields in the presence of 2-hydroxypyridine. The polycondensation reaction of the biscarbamates with diols was facilitated by catalysts such as metal salts; among the catalysts examined magnesium chloride in pyridine gave the best results. Metal chlorides in pyridine also promoted the reaction of DPC with aromatic amines to give the corresponding ureas, and the direct synthesis of polyureas was achieved by the polycondensation of DPC with diamines in the presence of the chloride.
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  • 52
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl methacrylate (MMA) and styrene (St) copolymerize in the presence of zinc chloride at 3°C under photoirradiation. The contents of methyl methacrylate in the copolymers obtained at a [ZnCl2]/[MMA] molar ratio of 0.4 are systematically larger than 53 mole %, which is the limiting value at a small feed ratio of methyl methacrylate. The resulting copolymers are confirmed as the sole products and not the mixtures by thin layer chromatography. The effect of dilution of the monomer feed mixture with toluene on copolymer composition suggests that it depends chiefly on the feed concentration of styrene and hardly at all on monomer feed ratios. Copolymerizations are also conducted in the presence of stannic chloride at -17°C under photoirradiation and in the presence of ethylaluminium sesquichloride at 0°C with spontaneous initiation. The contents of methyl methacrylate in both copolymers obtained at feed ratios lower than 60 mole % almost correspond to the 1:1 alternating copolymer and increase systematically with higher feed ratios. The systematic deviations of copolymer composition obtained in the presence of metal halides are reasonably interpreted by the participation of the binary molecular complex composed of metal halide and methyl methacrylate in the polymerization of the ternary molecular complex composed of metal halide, methyl methacrylate, and styrene.
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  • 53
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 877-888 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of the 1:2 copolymer of divinyl ether and maleic anhydride was investigated by 13C-NMR spectroscopy. The polymer contains the bicyclic unit composed of one molecule of each monomer and the maleic anhydride unit. The carbon chemical shift for these units was calculated on the basis of the chemical shift of many model compounds. The major peaks of the cyclopolymer prepared in chloroform were consistent with the presence of the symmetrical bicyclic unit with cis junction and the trans monocyclic anhydride unit. The carbonyl carbon spectrum for the copolymer obtained in a mixed solvent of acetone and CS2 suggested the predominant formation of the unsymmetrical bicyclic unit. The polymerization process was discussed on the basis of these results.
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  • 54
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1103-1116 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The excited state of pyrene observed in fluorescence and pulsed laser techniques is used to show that pyrene is solubilized in the polymer coil of aqueous solution of polymethacrylic acid (PMA) at pH 〈 4-5. This leads to a decreased access of molecules such as I-, Tl+, CH3NO2, and O2 to excited pyrene in the polymer coil. The protection of the excited state by solubilization in the polymer is sufficient to enable 3-bromopyrene phosphorescence to be observed at room temperature in these systems. Increasing the pH of the system uncoils the polymer and leads to increased accessibility of excited pyrene to CH3NO2; eventually, at pH 〉5, the pyrene is ejected into the aqueous phase of the system. In the presence of micellar solutions of surfactants increasing pH transports the pyrene from the polymer to the micellar aggregates. These fluorescence techniques are used to investigate the kinetics of expansion of the polymer coil. The system is suggested as a suitable model for the interaction of pyrene with biopolymers such as DNA.
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  • 55
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1129-1144 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have screened various multifunctional Friedel-Crafts alkylation and acylation reagents for their charring ability in impact polystyrene. Only benzyl chloride reagents with Sb2O3-halogen catalysts promoted crosslinking; the result is increased char yields and decreased fuel production and thereby improved fire resistance. Selected systems were evaluated for ignition, extinction, flamespread, and smoke generation; chars were fully characterized.
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  • 56
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1153-1161 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To elucidate mechanisms in electroinitiated polymerization reactions a comparison was conducted between ultraviolet (UV) photoinitiation and electroinitiation of N-vinyl phthalimide with zinc chloride as a catalyst. Both methods give low yields of a complex polymer product. A detailed analysis, infrared (IR), gel permeation chromatography (GPC), elemental, and molecular weight, conducted on the polymeric products, indicated that phthalimide ring opening was occurring and that complex mixtures of poly(N-vinyl phthalimide) derivatives were formed. Both initiation methods gave comparable results, which further indicated mechanistic similarity between photo-and electroinitiation in these donor-acceptor charge transfer polymerizations.
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  • 57
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1175-1186 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electronic structure of a clean copolymer of ethylene and tetrafluoroethylene is investigated by measuring the ESCA spectra of the core and valence levels. The chemical composition and alternating (〉95%) structure of the copolymer, characterized separately by classical methods, is verified by analyzing the C 1s core-level spectrum. The comparison of the experimental valence band with an original EHCO band-structure calculation, and with similar data for a model of polymer with block structure, shows that the combined methods allow us to distinguish between the two compounds through their valence-band spectra.
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  • 58
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1235-1238 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 59
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1199-1213 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When a cation exchange membrane is immersed in a cationic polyelectrolyte solution to form a thin layer on the membrane surface, the membrane properties are changed: permselectivity between cations with different electric charges (a relative transport number of the calcium ions to sodium ions, PNaCa), current efficiency, and electric resistance of the membrane. Here the more compact the cationic polyelectrolyte layer, the more outstanding the change in permselectivity. To make a more compact layer, an electrodeposition method was adopted and a change in the permselectivity of the resultant cation exchange membrane was investigated. By using the electrodeposition method a strongly basic polyelectrolyte with a larger molecular weight effectively changed the permselectivity of the cation exchange membrane: the PNaCa value dropped to about 0.3 from about 2.5 of the PNaCa of the untreated membrane during electrodialysis of the sodium chloride - calcium chloride system, and an increase in the electric resistance of the membrane (i.e., organic fouling) due to a cationic surface-active agent could be prevented. It is noteworthy that by using the strongly basic polyelectrolyte with a larger molecular weight the electrodeposition method was effective, whereas the immersion method was ineffective. Furthermore, even with the electrodeposition method the cationic polyelectrolyte which had a relatively smaller molecular weight resulted in a more remarkable change in the PNaCa value than did that with a larger molecular weight. In the electrodeposition method the amount of polyelectrolyte cohered onto the membrane surface in creased with an increase in the concentration of the polyelectrolyte, and weakly basic polyelectrolyte, and weakly basic polyelectroyte (polyethyleneimine) was also available independent of its molecular weight.
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  • 60
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1247-1248 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1249-1249 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 62
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3183-3191 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Among the four 1,1-disubstituted 2-vinylcyclopropanes, diethyl 2-vinylcyclopropane-1,1-dicarboxylate (Ia), 2-vinylcyclopropane-1,1-dicarbonitrile (Ib), ethyl 1-cyano-2-vinylcyclopropanecarboxylate (Ic), and 1,1-diphenyl-2-vinylcyclopropane (Id), Ib and Ic polymerized well with sodium cyanide in N,N-dimethylformamide. Ib was most reactive and a polymer (IIb) from Ib exhibited an inherent viscosity of 1.05 dl/g (concentration of 1.0 g in 100 ml of 95% H2SO4). All experimental results indicated that the polymerization proceeded by ring opening and that the structure of the polymers had pendant vinyl groups. The polymer IIc from Ic was soluble in common solvents like acetone, but IIb was soluble only in 95% H2SO4. Reactions of those compounds with benzenethiolate ion in ethanol yielded addition products that supported the ring-opening polymerization of those monomers. In the postulated mechanism of polymerization cyanide ion attacks the carbon of a cyclopropane ring with electron-releasing vinyl group and the resulting anion is thereby stabilized by two electron-withdrawing substituents. The propagation takes place by the reaction of the anion with another monomer molecule.
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  • 63
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3217-3239 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Esterification-hydrolysis and condensation-glycolysis are the principal equilibria entailed in a system comprised of benzoic acid, ethanediol, ethanediol monobenzoate, ethanediol dibenzoate, and water. These equilibria are characterized by three interrelated equilibrium constants that pertain to the hydrolysis of both ethanediol monobenzoate and ethanediol dibenzoate and to the condensation of ethanediol monobenzoate. The rate constants related to these reactions and to the corresponding reverse reactions were all found to be functions of the concentration of carboxy groups. Antimony triacetate, a well-known transesterification catalyst, catalyzed the condensation reaction strongly but did not affect the esterification reaction. Based on a mechanism that entailed the considered three principal equilibrium reactions, a set of both the kinetic and thermodynamic parameters was obtained by a nonlinear regression procedure. With these parameters the nonlinear rate equations were integrated numerically, using the fourth-order Runge-Kutta method. Excellent agreement between the values thus calculated and the experimental data were obtained in all cases except when considerable concentrations of both benzoic acid and ethanediol dibenzoate were present in the system. It has been concluded that in these instances the formation of the dibenzoate is paralleled by a pyrolysis reaction that is strongly catalyzed by carboxy groups.
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  • 64
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3273-3278 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transfer constants to monomer at 55°C have been measured in 2 and 4-vinylpyridine radical polymerizations. In addition, the transfer constants to ethanol, octan-1-ol, toluene, benzyl alcohol, chloroform, and nitroethane have been measured. These values, which increase in the order above, show no significant variation between the two isomeric monomers.
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  • 65
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3241-3254 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The process of esterification of terephthalic acid is characterized by a mechanism that involves three equilibrium reactions. Two are esterification-hydrolysis equilibria entailing the reactions of the two terephthalic acid carboxyl groups with alcoholic hydroxyl groups, whereas the third one is a transesterification-acidolysis equilibrium that is concerned with the reaction between two terminal terephthalic acid moieties. The products of these three interrelated equilibria are terephthalic acid, its monoester and diester, the particular alcohol, and water. The alcohol used in the present study was 2-(2-methoxyethoxy)ethanol. Equilibrium constants and rate constants were developed from experimental data obtained at 230°C. The esterification-hydrolysis reactions were found to be catalyzed by carboxyl groups, and the rate of transesterification was found to be a function of the terephthalic acid concentration. With the constants developed, the system of nonlinear differential equations, as derived from the mechanism postulated, was integrated numerically using the Runge-Kutta method. Good agreement between calculated and experimental values was observed.
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  • 66
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3255-3271 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N,N′-(pyromellitoyl)diglycine (1) was synthesized by reacting pyromellitic anhydride with glycine in polar solvents such as DMAC, NMP, or DMF at 60°C and then refluxed azeotropically with toluene. Among these solvents, it is easy to form DMF-insoluble salt (1″) in DMF, but this salt can be converted to 1 by treating first with NaHCO3 and then with HCl. Reacting monomer N,N′-(pyromellitoyl)diaminoacetyl chloride (2) can be obtained by treating with thionyl chloride, and N,N′-(pyromellitoyl)dimethyl aminoacetate (3) can be obtained by treating 2 with methanol. As 2 reacts with aromatic diamine in polar solvents, such as DMAC, DMF, or NMP, a series of copolypyromellitimide amides (5a-h) can be obtained. These copolymers can be processed by using DMAC + LiCl (5%) as solvent to produce flexible film of good weather resistivity and heat resistivity. Monomer 2 can also react with aromatic dihydrazides in polar solvents to produce copolypyromellitimide hydrazides (6a-c), and 6a-b can be condensated again to produce copolypyromellitimide oxadiazoles (7a-b) in polyphosphoric acid (PPA). Besides, 3 reacts with aromatic tetraamine by carrying out polycondensation in PPA to produce copolypyromellitimide benzimidazole (8). Structures of copolymers mentioned above were identified by comparing IR spectra with those of model compounds. Heat resistivity was measured by the thermogravimetric method, and their solubilities in various solvents were also investigated.
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  • 67
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3291-3295 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-initiated graft polymerization of 4-vinylpyridine to high-density polyethylene has been studied under diffusion-free conditions by the mutual irradiation technique. The reaction rate is 1/2 order in radiation intensity over the range 0.00076-0.011 Mrad/hr. The reaction rate is first order in monomer at 0.00076 Mrad/hr, over the complete range of monomer concentrations; at 0.021 Mrad/hr, up to 60 vol % monomer; and at 0.21 Mrad/hr, up to 50 vol % monomer.
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  • 68
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3279-3289 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several copolymers of 2-hydroxyethyl methacrylate (HEMA) with methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (BA), and methyl methacrylate (MMA) were prepared at 70°C in nitrogen atmosphere using 0.2% (w/v) benzoyl peroxide as initiator. The copolymer composition was evaluated by estimation of hydroxyl group in the copolymers. Intrinsic viscosity of HEMA-EA, HEMA-BA, and HEMA-MMA copolymers was determined at 35°C in dimethyl formamide. Molecular weight distribution of copolymer samples was evaluated by gel permeation chromatography. Thermal behavior of the copolymers was investigated by dynamic thermogravimetry. Thermal stability decreased on increasing HEMA content in MA, EA, and BA copolymers. However, a reverse trend was observed in HEMA-MMA copolymers.
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  • 69
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1483-1491 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Wholly aromatic polysulfonamides of high molecular weight were prepared by the solution poly-condensation of aromatic disulfonyl chlorides with aromatic diamines in tetramethylene sulfone and substituted pyridines as the acid acceptor. Polysulfonamides with inherent viscosities as high as 1.2 were readily obtained by initiating polycondensation at a temperature of 5-10°C to control the side reactions. The polycondensation was fairly fast and was completed in 10 min at 60°C. All the aromatic polysulfonamides dissolved in a wide range of solvents, including acetone and tetrahydrofuran. These polymers were less thermally stable than the corresponding aromatic polyamides.
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1557-1563 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1565-1568 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 72
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1583-1593 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stereoelective polymerization of racemic t-butyl thiirane was performed with chiral zinc glycolate. Monomers and polymers of high optical purities were isolated. A new kinetic scheme in which the ratio of the rates of consumption of both enantiomers obeys a second-order relationship is proposed. This behavior is different from that observed for other three-membered ring monomers.
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  • 73
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1595-1604 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of enantiomerically enriched t-butyl thiirane was studied. The stereoelectivity and the kinetic behavior are not changed when a monomer of an initial enantiomeric composition lower than a defined limit value is used. When the enantiomeric composition is higher than this value, the stereoelectivity increases. In agreement with kinetic results, a mechanism is proposed involving, in a first step, the complexation of monomer on preexisting sites of the initiator with formation of highly selective chiral active species on which propagation occurs.
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  • 74
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1619-1629 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyurethanes were synthesized by polyaddition reaction of bis-N-hydroxyimides and diisocyanates. The reactions were carried out in an aprotic polar solvent such as dimethylacetamide or N-methyl-2-pyrrolidone, and the polymers with inherent viscosities of up to 1.32 dl/g were obtained. These polyurethanes were found to exhibit high reactivity toward nucleophiles such as water and amines, which brought about rapid reduction of viscosity. The stabilities against heat and exposure to sunlight were also studied.
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  • 75
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1645-1653 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The initiation quantum yield in the bulk photopolymerization of vinyl monomers sensitized by 2,4-dimethyl-3-pentanone has been measured for several monomers. The results obtained were interpreted in terms of a mechanism that considers singlet and triplet photocleavage of the ketone, competing with the quenching by the monomer. The quenching process does not lead to free radicals that can initiate the polymerization.
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  • 76
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1779-1788 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The homogeneous catalyst Re(CO)5X (X = Cl, Br) was found to promote the homopolymerization of terminal alkynes at elevated temperatures. Detection and structure characterization of low-molecular-weight products provided evidence of the formation of a metal-acetylide species as the initiator of polymerization, and propagation occurs by a series of insertion reactions of coordinated alkynes into metal-carbon bonds of the growing chain. Evidence of the active forms of the catalyst comes from studies on gas evolution, catalyst derivatization, and copolymerization reactions. The final polymers have a linear, polyconjugated macrostructure, and the formation of aromatic species was not detected in these reactions.
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  • 77
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1771-1777 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found that N,N,N′,N′-tetramethylethylene diamine and hexamethyl phosphorus triamide minimize chain transfer reactions in the polymerization of 1,3-butadiene in hydrocarbon solvent with alkylsodium or alkylpotassium initiators. The polymers obtained with alkylsodium initiators had a high molecular weight and high vinyl content at 90-95% conversion. The molecular weight of the polybutadiene made by alkylsodium and alkylpotassium initiators was dependent on the polymerization temperatures and modifier ratios, but the vinyl contents were independent of the modifier ratios. Vinyl contents of alkylpotassium-initiated polymers showed a slight dependency on polymerization temperature; the vinyl contents of alkylsodium-initiated polymers were independent of temperature. Addition of lithium tert-butoxide and potassium tert-amylate to these initiators in the presence of the modifiers affected the molecular weight but not the microstructure.
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  • 78
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1789-1793 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymerization of methyl trifluoroacrylate (MTFA) with ethylene in bulk was induced by γ irradiation. The copolymerization was observed to proceed in the liquid monomer mixture of MTFA and ethylene at 25°C with the dose rates ranging from 5.0 × 104 to 1.0 × 106 rad/hr. A wide range of the initial monomer composition gives an almost equimolar and alternating copolymer. The highest polymerization rate was observed at the equimolar monomer composition. The dose rate exponent of the polymerization rate is unity. The reactivity ratios of r1 (MTFA) and r2 (ethylene) were determined to be 0.034 and 0.14, respectively.
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  • 79
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3509-3518 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of the lithium enolates of cyclopentadiene-blocked acrylates with various electrophilic reagents, such as alkyl chloroformates, α,β-unsaturated carbonyl compounds, epoxides, episulfides, and α-halocarbonyl compounds, has led to a convenient synthetic method for the preparation of α-substituted acrylic esters.
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  • 80
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1811-1819 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The scattering function of rods with a constant radius, 8 Å, and a length distribution of the Schulz-Zimm type was calculated on a computer as a model of helical synthetic polypeptide. The influence of length and length distribution on the scattered intensity of small-angle x-ray scattering was clarified. As length grows and length distribution broadens it is difficult to obtain reliable values of molecular weight and radius of gyration from a Zimm plot. The influence of length distribution on the mass per unit length, Mq, and the radius of gyration of the cross section, 〈Sq2〉1/2, from the Guinier plot of the cross-sectional factor decreases as the length increases, and reliable values of Mq and 〈Sq2〉1/2 can be obtained even for rods with wide distribution for rods more than 600 Å long. In particular, it is pointed out that the value of 〈Sq2〉1/2 is little influenced by length and length distribution.
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  • 81
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1821-1827 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bulk viscosity of polymethylhydrogensiloxane containing methoxy groups (PMHS-A) was measured before and after irradiation. The gel point was then determined from the variation of viscosity by irradiation by comparing it with methoxy-free polymethylhydrogensiloxane (PMHS-B) and polydimethylsiloxane blocked by methoxyldimethylsilyl (PDMS-C) or trimethylsilyl (PDMS-D). The following results were obtained: (1) The G value of crosslinking by irradiation is 167, 52, 25, and 3 for PMHS-A, PMHS-B, PDMS-C, and PDMS-D, respectively. (2) The scission of the SiO—CH3 bond is easier than that of the Si—H, Si—CH3, or SiCH2—H bond. The SiO—CH3 bond is PMHS-A is severed from SiO· and ·CH3 to induce chain reactions at the initial stage by irradiation. (3) It was confirmed that the commercial PMHS is at present free of methoxy groups. To replace the hydrogen of Si—H in the commercial PMHS with methoxy groups heat treatment with methanol was performed by which the G value of crosslinking was increased.
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  • 82
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1843-1845 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 83
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1883-1886 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 84
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1887-1888 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 85
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1901-1909 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ring-opening polyaddition of N,N′-arylenedisulfonylbissuccinimides with both aliphatic and aromatic diamines in N-methyl-2-pyrrolidone at room temperature afforded polyacylsulfonamide-amides having inherent viscosities in the range of 0.2-0.4 in excellent yields. The polymers revealed acidic nature and were readily soluble in both polar aprotic solvents and basic media. They melted at a temperature below 200°C and began to decompose at around 250°C in nitrogen.
    Additional Material: 3 Ill.
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  • 86
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1891-1900 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gel effect in free radical polymerization of vinyl monomers has been recognized as the result of the increased viscosity of the reaction solution of polymer in monomer, which causes a decrease in the rate of the termination reaction. This effect manifests itself as an increase in the rate of polymerization over that rate to be expected in its absence. Definition of the onset of the gel effect has become necessary for several purposes. Previously, it has been common to define the onset phenomenologically, i.e., in terms of the increase in the rate of polymerization. It is proposed here that the onset of the gel effect is best defined on a fundamental basis, i.e., as occurring at that conversion at which the rate of segmental diffusion of the polymeric radicals equals the rate of their translational diffusion. Experimental evidence is presented that shows that the small minima predicted by this definition do exist for both rates and degrees of polymerization. Measurements of the viscosities of solutions of polymers in their monomers suggest that the polymer concentrations at which the “chain-entanglement” phenomena are observed are the same as those for the onset of the gel effect for styrene, methyl methacrylate, and butyl methacrylate.
    Additional Material: 9 Ill.
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  • 87
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1911-1921 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: α-Isobutyl-L-aspartate oligomers, Z-(α-i-Bu-Asp)2n-OEt (n = 1-5), where Z = benzyloxycarbonyl and OEt = ethyl ester, were prepared stepwise, and their conformation in solution was investigated by optical rotation, circular dichroism (CD), and NMR spectroscopy. The oligomers up to hexamer existed only in a disordered form. An ordered structure began to appear at octamer and decamer in chloroform and 2,2,2-trifluoroethanol. The ordered structure was more favorable for N-unprotected oligomers, H-(α-i-Bu-Asp)2n-OEt, in comparison with the corresponding Z-(α-i-Bu-Asp)2n-OEt. The effects of oligomer concentration and temperature on the structure were slightly observed. The most likely ordered structure was a β form caused by intramolecular association.
    Additional Material: 7 Ill.
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  • 88
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1923-1944 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crystalline poly(n-nonaldehyde) (PNA) was prepared by anionic polymerization of n-nonaldehyde (NA) in methylcyclohexane (MCH) with lithium tertiary butoxide (LTB) as the initiator. Normal low-temperature conditions did not give polymer reprodusibly; however, when the polymerization was carried out with a gradual temperature decrease to -60°C holding at this temperature followed by completion at -78°C, a moderate yield of PNA was obtained. The polymer was acetate capped and characterized. Infrared and PMR spectroscopy, as well as degradation of the polymer in the presence of 2,4-dinitrophenylhydrazine to the hydrazone, conclusively proved the chemical structure of the polymer. VPO measurements and measurement of the inherent viscosity showed the polymer to be of moderate molecular weight. PNA is highly crystalline and shows two transition regions, one corresponding to the melting of the main chain at temperatures above 120°C and one region between 50 and 80°C, which is related to the crystallization of the aliphatic side chains. PNA, although inherently brittle, can be extruded through an orifice at a temperature near the side-chain melting temperature to give an extrudate whose x-ray patterns show the characteristics of a fiber diagram. It is suggested that the crystal structure of the PNA is similar to that of poly(n-heptaldehyde) but with a larger a spacing, which is expected from a longer aliphatic side chain.
    Additional Material: 6 Ill.
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  • 89
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1945-1951 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Representatives of a family of soluble, imidized maleimide-terminated amide-imide precursors for molding and composite applications were prepared and characterized. The key step was the preparation of an amine-terminated amide-imide intermediate that was needed in order to introduce the maleimide groups. Trimellitic anhydride (TMA) and its monoacid chloride (TMAC) were each investigated for utility in reaction with molar excesses of methylenedianiline. With TMA the limiting factor was the time-consuming amidation reaction, which, although catalyzed with triphenyl phosphite, required 24 hr to bring to completion in hot N-methylpyrrolidone (NMP). The use of TMAC provided a more facile route to the intermediate and, as shown by gel permeation chromatography (GPC), resulted in a narrower molecular weight range than with TMA for the final maleimide-terminated products. The reactions were followed by carboxyl titration, and the resulting products were characterized by IR, NMR, DTA, GPC, and inherent viscosity. The relative thermal capabilities were compared by isothermal aging as thin films (250°C) and as molded bars (316°C). Physical properties were assessed on glass laminates and molded bars. Although soluble in polar solvents, the products were viscosity unstable at ambient conditions. A solution to this problem was demonstrated by the preparation of the cyclopentadiene adduct, which was viscosity stable.
    Additional Material: 4 Ill.
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  • 90
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1953-1961 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermodynamic parameters for the interaction of the hydrophobic fluorescent probe, 2-p-toluidinylnaphthalene-6-sulfonate (TNS), and polycations that contain a piperidinium cation and various nonpolar pendant groups were calculated. Binding is exothermic and involves a positive entropy gain. The contribution of the entropy term to the free energy change tends to increase with increasing hydrophobicity of the polymers. The intensity of the fluorescence of TNS is enhanced when the probe binds to the polycations. The nature and phenomena of hydrophobic fluorescent probe binding with the polymers are discussed.
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  • 91
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1963-1976 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thiophene was polymerized in high yield on exposure to aluminum chloride in solvent under mild conditions. Experimental evidence [IR, NMR, UV, and mass spectra, elemental analyses, reductive desulfurization, and comparison with the literature trimer of thiophene (prepared with phosphoric acid)] suggests the following structure: From gel permeation chromatography an average weight of 1290 was obtained, which corresponded to the presence of 15 rings; the highest-molecular-weight chains contained about 192 rings. Mechanistically, participation of cationic intermediates is proposed. Apparently chain extension can occur by various routes, including participation of neutral oligomer molecules.
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  • 92
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1977-1990 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic variables associated with the hydrolysis of linear poly[(acylimino)ethylenes] by acid and base have been studied. As anticipated, both reactions follow conventional second-order rate laws and are essentially irreversible. This stoichiometry and the unexpectedly rapid rate of the acid hydrolysis have been useful in the preparation of partly deacylated poly[(acylimino)ethylenes]. The desired degree of deacylation can be accurately obtained by the relative amount of acid and hydrolyzable amide functionality. The effects of the reaction temperature and nature of the acyl group on the reaction rate have been determined and an unusual relationship between rate and molecular weight was uncovered. The reactions are compared with the hydrolyses of corresponding monomeric tertiary amides and the potential utility of the products is discussed.
    Additional Material: 5 Ill.
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  • 93
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3785-3792 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 94
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3797-3810 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several N-vinylarylamines have been prepared by direct N-vinylation of arylamine salts with acetylene at atmospheric pressure. Nuclear magnetic resonance (NMR) spectra of the various N-vinylarylamines were recorded and chemical shift assignments were made for the first time. The vinyl protons of the enamines generally exhibit an ABX pattern. The electron-rich monomers are sensitive to acid-catalyzed hydrolysis in a wet solvent. Polymerizations of the monomers were carried out at low temperatures with phosphorous pentafluoride as an initiator. It was found that PF5 generated directly from thermal decomposition of p-chlorobenzenediazonium hexafluorophosphate is useful in the preparation of an extremely high-molecular-weight poly(N-vinylcarbazole) (Mw = 3 × 106) with a narrow molecular weight distribution (MWD = 2.1). The polymerizability of N-vinylarylamines appears to vary with the amine functional groups of the monomers. N-vinylarylamine containing a planar amine moiety such as carbazole forms a higher-molecular-weight polymer than the monomers with the nonplanar bulky amine groups.
    Additional Material: 1 Ill.
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  • 95
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3823-3833 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The alternating copolymerization of 1- and 2-vinylnaphthalene (1-VNap and 2-VNap) with methyl methacrylate (MMA) by using diethylaluminum chloride (Et2AlCl) in toluene at 0°C has been studied. No polymerization could occur without Et2AlCl, and alternating copolymers were obtained only when an equimolar amount of Et2AlCl with MMA was supplied. Through 1H-NMR analyses on both dyad and triad of alternating deuterated 1- and 2-α-d-VNap-MMA copolymers, each configuration could be described successfully by a single parameter, coisotacticity σ, whose value was estimated as 0.41 for the former and 0.56 for the latter copolymer, respectively. A rather low coisotacticity of copoly(1-VNap-MMA) was explained in the terms of steric effect (peri effect) of 1-VNap monomer.
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  • 96
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3811-3821 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New polythioesters of naphthalene derivatives by polycondensation of 1,4-di(mercaptomethyl)-naphthalene, 1,5-di(mercaptomethyl)naphthalene, as well as their mixture with adipoyl and sebacoyl chlorides have been obtained. Low-temperature and high-temperature solution polycondensation as well as interfacial polycondensation have been used. Interfacial polycondensation proved to be the most useful. To define the optimal conditions of interfacial polycondensation, the following factors influencing the process have been studied: ratio of aqueous to organic phase, concentration of hydrochloride acceptor, temperature of reaction and rate of addition of acid chloride, contribution of emulsifier and catalyst. Yield for all reaction products and reduced viscosity have been found. The structure of polythioesters of high-value viscosity and good yield was determined from elementary analysis, infrared spectra, x-ray, and thermogravimetric analysis. Some mechanical and electrical properties of the polythioesters obtained from the mixture of 1,4- and 1,5-di(mercaptomethyl)naphthalene have been studied after pressing in increased temperature. The molecular weight was not determined because of very low solubility.
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  • 97
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3835-3844 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equilibrium constants of the charge-transfer complex monomers of phenylvinyl alkyl ethers (I) and thioethers (II) with maleic anhydride (MAn) were determined by the transformed Benessi - Hildebrand NMR method, and it was found that the bulkiness of alkyl groups had no significant influence on the equilibrium constant. The rate of copolymerization, however, was largely dependent on the bulkiness of the alkyl groups in the phenylvinyl alkyl ether series. The rate of copolymerization of I (R = Et; sec-Bu) and II (R = Et; sec-Bu) with MAn was proportional to the square root of AIBN concentration, and intrinsic viscosity of poly-I (R = Et)-co-MAn was proportional to the reciprocal square root of AIBN concentration. Spontaneous copolymerization did not occur, but I (R = Et) copolymerizes with MAn in the presence of oxygen; II did not copolymerize with MAn in the presence of oxygen; nor in the presence of peroxide initiators. In the copolymerization of I (R = Et) and MAn, it was found that molecular weight increases with conversion. By applying the generalized model described by Shirota and co-workers, the reactivity ratios k1c/k12 and k2c/21 for copolymerization of I (R = Et) and II (R = Et) with MAn were calculated from the change of copolymerization rate with monomer feed at constant total monomer concentration.
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  • 98
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3845-3858 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photosensitive polyimidothioethers were prepared by the base-catalyzed condensation of bisthiols with 4,4′-(N-maleimido)diphenyliodonium chloride. Copolymers with other bismaleimide monomers were also prepared. The ultraviolet-induced degradation of two of the copolymers was studied and the effects of light intensity on the rate of photolysis determined. It was also demonstrated that the range of spectral sensitivity of these polymers can be extended into the visible region through the use of dye sensitizers.
    Additional Material: 9 Ill.
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  • 99
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3859-3866 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The present investigation describes a new approach for the determination of radical substituent parameters σ. The technique has been developed by an ingenious combination of two equations, one proposed by Yamamoto and Otsu and the other by Streitwieser and Perrin. The σ values for different substituents were first evaluated by application of this newly developed technique to the Ce(IV)-substituted toluenes-acrylonitrile system. The validity of these values was then tested by application to another system, the Ce(IV)-substituted acetophenones-acrylonitrile system, which is the subject of the present study.
    Additional Material: 3 Ill.
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  • 100
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    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 2093-2101 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of an optical active amyloxyaluminum or menthoxyaluminum chloride the asymmetric-induction alternating copolymerization of benzofuran or 1,3-cyclooctadiene and acrylonitrile or methacrylonitrile was investigated. The sign of optical rotation of copolymers was positive or negative, depending on the kind of catalyst used. The optical activity of copolymers of benzofuran and acrylonitrile attains a maximum value at an equimolar composition. The highest specific rotation [α]D of copolymers of benzofuran and acrylonitrile prepared in the presence of stoichiometric amount of ( - )-menthoxyaluminum dichloride with respect to acrylonitrile was about -8°. The stereo-structure of acrylonitrile unit may be controlled by the optical active aluminum compound onto which a strong coordination of acrylonitrile may occur.
    Additional Material: 5 Tab.
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