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  • 2000-2004
  • 1980-1984  (652)
  • 1983  (652)
  • Physics  (538)
  • pharmacokinetics  (114)
  • 101
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 24 (1983), S. 7-14 
    ISSN: 1432-1041
    Keywords: oxprenolol ; coronary heart disease ; normals ; pharmacodynamics ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The plasma concentration profile of oxprenolol after intravenous bolus injection, during intravenous infusion and following sustained oral administration was studied in a total of 106 patients with coronary heart disease. Speed of onset of pharmacodynamic activity, as measured by suppression of isoprenaline tachycardia, was discernible within a few seconds of central injection and complete within 5 min in all patients; variability in response was small. Following both i.v. bolus and intravenous infusion, plasma oxprenolol concentrations showed considerable between patient variability The plasma concentration/time profile observed in 16 patients following single intravenous oxprenolol bolus therapy was substantially higher, particularly during the early distribution phase, than observed and predicted volunteer data. Higher plasma oxprenolol concentrations were also attained during the more extended time sampling of the infusion studies; these findings would be compatible with reduced oxprenolol clearance in patients with ischaemic heart disease. During chronic oral therapy there was a many-fold between-subject variability in plasma concentration achieved following a given ingested dose. Correlation of antagonism of exercise tachycardia inhibition with plasma oxprenolol concentration in 15 male volunteers demonstrated near complete blockade of exercise stimulation of chronotropic beta-adrenoceptors at an average plasma oxprenolol concentration of 150 ng/ml. In coronary heart disease, such plasma concentrations can most conveniently be achieved by a 4 mg oxprenolol intravenous bolus with simultaneous infusion of 0.05 mg/kg/h; however, these studies provide sufficient information to allow alternative regimens to be derived should lesser plasma concentrations be considered desirable.
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  • 102
    Electronic Resource
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    Springer
    European journal of clinical pharmacology 24 (1983), S. 209-215 
    ISSN: 1432-1041
    Keywords: sobrerol ; mucus liquefaction ; pharmacokinetics ; bronchial mucus level ; mass fragmentography ; metabolites
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetic profile of Sobrerol, a mucolytic drug, has been studied in patients with acute exacerbations of chronic bronchitis and dense sputum. In addition to measurement of serum and urine levels, the concentration in bronchial mucus was also examined, and their correlation was calculated. Mass fragmentographic analysis was used to assay free sobrerol and its principal urinary metabolites hydrated carvone and glucuronidated sobrerol. After the doses and administration routes used, there appeared to be accumulation of sobrerol in bronchial mucus. This is a feature of great interest and value for a drug which has the specific action of liquefying mucus.
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  • 103
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    Springer
    Investigational new drugs 1 (1983), S. 47-58 
    ISSN: 1573-0646
    Keywords: dihydro-5-azacytidine ; DHAC ; pharmacokinetics ; clearance ; foxhound
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary An HPLC analytical method was applied to the determination of plasma concentrations of 5,6-dihydro-5-azacytidine (NSC 264880, DHAC) in two foxhounds after a rapid intravenous infusion of 300 mg/kg DHAC. The dose employed is the mouse equivalent LD10 dose which results in mild reversible toxicity in the dog. The decline in DHAC plasma concentrations was greater than three log decades after dosing. The plasma concentration-time data was computer-fitted by NONLIN to a three compartment open model with first-order elimination using the equations for a short intravenous infusion. The half-lives corresponding to the three exponential phases were: t1/2α =5.78 min, t1/2β =1.57 h and t1/2γ =22.0 h in dog 1 and t1/2α =7.41 min, t1/2β =2.25 h and t1/2γ =21.6 h in dog 2. The terminal phase of the plasma concentration time profiles represented a minor contribution (2.2–3.2%) to the total area under the curve. The plasma concentration time data for the first 12 h after dosing was computer fitted to a two compartment open model. The initial and terminal half-lives determined from the two compartment fits were similar to the t1/2α and t1/2β values of the fits to the three compartment open model. Similar total body clearance values were calculated from the areas under the plasma concentration time curves from time zero to infinity for the computer fits to the three and two compartment models, respectively. Thus, for practical purposes, it appears feasible to define adequately the total body clearance of DHAC by analysis of the plasma concentration time data during the time interval in which the plasma concentration is described as a bi-exponential equation. Renal excretion of the parent drug is the principal route of excretion of DHAC from the dog.
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  • 104
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    Springer
    Journal of pharmacokinetics and pharmacodynamics 11 (1983), S. 499-513 
    ISSN: 1573-8744
    Keywords: methotrexate ; 7-hydroxy-methotrexate ; pharmacokinetics ; nonlinear pharmacokinetics ; dose-dependent pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pharmacokinetics of methotrexate (MTX) and 7-hydroxy-methotrexate (7-OH-MTX), a major metabolite, were investigated in rabbits after intravenous bolus injection and infusion using a specific HPLC assay. The arterial sampling (from the carotid artery) was used in all the studies since peculiar and significant arterial-venous differences in the plasma concentration of MTX and 7-OH-MTX were found following bolus administration of the drug. The disposition kinetics of MTX appeared polyexponential with a small terminal phase having a half-life of 10.2–27.5 hr. Extensive formation of 7-OH-MTX occurred at the two dose levels (15 and 50 mg/kg). Nonlinear disposition of MTX was reflected in several aspects of data analysis. A disproportionate increase in the AUC with dose was observed. An increase in dose not only reduced the mean total body clearance (7.49 vs. 4.26 ml/min/kg) and renal clearance (4.89 vs. 2.76 ml/min/kg), but also prolonged the mean residence time (26.2 vs. 43.3 min). The steady-state volume of distribution (Vss) of MTX was estimated to range from 0.16 to 0.25 L/kg. More than 90% of the dose was excreted as MTX and 7-OH-MTX within 8 hr after dosing. Renal clearances decreased with the increasing plasma levels, suggesting active tubular secretion as one of the excretion mechanisms. A similar pattern for renal clearance of 7-OH-MTX was obtained. Infusion studies of 7-OH-MTX revealed that this metabolite had a longer residence time and a larger Vss as compared with MTX, which were in accordance with its physicochemical properties. Essentially complete doses of 7-OH-MTX could be recovered in the rabbit urine.
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  • 105
    ISSN: 1573-8744
    Keywords: insulin ; continuous subcutaneous infusion ; plasma immunoreactive insulin ; pharmacokinetics ; preprogrammable infusion pump ; reconstruction of predetermined plasma insulin profiles ; dogs
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A preprogrammable insulin delivery system which can provide the flexibility of varying plasma insulin concentration in a physiological manner has been developed. This system involves a program of continuous subcutaneous infusion of insulin at variable rates to reproduce arbitrarily selected plasma insulin concentration-time profiles. The desired insulin infusion rate profile was calculated from the desired insulin pattern using pharmacokinetic parameters experimentally determined by measurement of immunoreactive plasma insulin following a subcutaneous bolus dose to depancreatized dogs.
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  • 106
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    Journal of pharmacokinetics and pharmacodynamics 11 (1983), S. 289-301 
    ISSN: 1573-8744
    Keywords: parameter estimation ; upper and lower bounds ; pharmacokinetics ; initial estimates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The upper and lower bounds of rate constants for general mammillary three and four compartment systems have been derived. It is further proposed that the midpoints of the bounds can be used as initial estimates for parameter estimation. Numerical examples are given demonstrating the closeness of the calculated midpoints to the “known” rate constants of both the three and four compartment systems.
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  • 107
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    Journal of pharmacokinetics and pharmacodynamics 11 (1983), S. 561-576 
    ISSN: 1573-8744
    Keywords: methylprednisolone ; bioavailability ; pharmacokinetics ; oral and parenteral administration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This study was conducted to evaluate the influence of route of administration upon the bioavailability and pharmacokinetics of methylprednisolone sodium succinate. Fourteen healthy adult male volunteers received 40 mg doses of methylprednisolone as the following treatments after an overnight fast in a 4-way crossover design: (a) as a 1 ml i.v. bolus;(b) as a 1 ml i.m. injection;(c) administered as an oral solution;and (d) as 5×8 mg oral tablets. Both the ester and free methylprednisolone were determined in plasma and urine. Study results indicate that the ester is rapidly and extensively converted to free methylprednisolone after all routes. The extent of methylprednisolone absorption was equivalent after i.v. and i.m. administration. Both orally administered treatments resulted in a lower extent of absorption attributed to a first-pass effect. Although a slightly lower extent of absorption was demonstrated following the oral administration of the methylprednisolone sodium succinate solution relative to the methylprednisolone oral tablets, this average difference of 9% would probably be of minimal therapeutic importance.
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  • 108
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    Journal of pharmacokinetics and pharmacodynamics 11 (1983), S. 183-187 
    ISSN: 1573-8744
    Keywords: nonlinear regression ; parameter estimation ; invariance ; transformation ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It is shown that when one nonlinear regression model is a reparametrization of a second model, the parameter estimates, and their standard errors, for one model can be obtained directly from those obtained from fitting the other model.
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  • 109
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    Journal of pharmacokinetics and pharmacodynamics 11 (1983), S. 389-400 
    ISSN: 1573-8744
    Keywords: time-dependence ; volume of distribution ; curve-fitting ; simulations ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The present study was conducted to develop, test, and apply a simple exponential time-dependent volume of distribution function to describe the pharmacokinetics of compounds following instantaneous, zero-order and first order input. Simulations were used to show the applicability and flexibility of the equations. Experimental data from the literature were fitted using the equations developed in the present study. In addition, the results of these fitted curves were compared to the results of the original fitting procedures to compare and contrast the methods. In the present analysis, the change from an initial volume (V1)to the total volume (VT)is perceived as a simple exponential function. Therefore, a single exponential term to describe elimination and a single exponential term to describe the change from V1 to VT were used to describe the entire blood concentration profile. The results from present simulations and fitted data indicate that the transition from V1 to VT is a more continuous process than observed with classical methods and is consistent with results obtained from physiologic flow-limited models. This observation suggests that the present curve-fitting technique may be more akin to physiologic reality, in that it depicts the change from the initial volume of distribution to the total volume of distribution as a continuous exponential function which reflects the establishment of an equilibrium.
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  • 110
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    Journal of pharmacokinetics and pharmacodynamics 11 (1983), S. 31-46 
    ISSN: 1573-8744
    Keywords: bumetanide ; probenedd ; pharmacokinetics ; pharmacodynamics ; doseresponse relationship
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pharmacokinetics and pharmacodynamics of intravenous bumetanide (0.250 mg/kg), alone (treatment I) and after probenecid pretreatment (treatment II), were studied in four mongrel dogs. Lactated Ringer's solution was administered by vein throughout both treatments at a flow rate of 2 ml/min to avoid fluid and electrolyte depletion. Bumetanide and probenecid concentrations were analyzed by HPLC, sodium by flame photometry, and creatinine by colorimetry. Although the probenecid markedly reduced the plasma and renal clearances of bumetanide, as well as the fraction excreted unchanged in the urine, there was no significant difference between treatments I and II in the 4-hr natriuretic and diuretic responses. However, analysis of the dose-response curves between treatments I and II showed that sodium, excretion was better correlated with bumetanide urinary excretion rate than with plasma concentration. The reasons for a poor correlation between treatments during the early time periods are discussed.
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  • 111
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    Journal of pharmacokinetics and pharmacodynamics 11 (1983), S. 47-61 
    ISSN: 1573-8744
    Keywords: d-tubocurarine ; pharmacokinetics ; pharmacodynamics ; multicompartrnent model ; Hill equation ; plasma ; tibialis anterior muscle ; protein binding ; rats
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract After bolus intravenous dosing of d-tubocurarine (d-TC) to rats, the twitch heights of the tibialis anterior muscle indirectly stimulated were followed, and its decrease was defined as pharmacologic response of d-TC. The relation between dose and response intensity was found to be well described with Hill's equation. According to a theory proposed by Smolen, Hill's equation was also applicable to the biophase d-TC concentration-response relation; the time courses of the relative biophase d-TC concentration indicated linear kinetics with dose levels ≤0.15 mg/kg and the occurrence of dose-dependent disposition with 0.30 mg/kg. After bolus i.v. dosing of3H-d-TC, plasma d-TC concentration obeyed a dose-independent two compartment model with doses ≤0.15mg/kg, but not with 0.30 mg/kg. This finding matched the above estimated with pharmacologic data. The active metabolite was not found in plasma and urine. The extent of d-TC plasma protein binding was independent of the wide range of plasma levels and its mean (±SD) value was 30.5 (±3.8). Plasma d-TC levels and pharmacologie response intensity were well correlated by Hill's equation and a three compartment model (the general two and the biophase compartments) in the dose range ≤0.15 mg/kg.
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  • 112
    ISSN: 1573-8744
    Keywords: naltrexone ; controlled release ; pharmacokinetics ; gas chromatography ; biodegradable copolymer delivery system ; release rate quantitationin vivo ; Loo-Riegelman method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Naltrexone release rates from a controlled release delivery system have been quantitated over a time period greater than one month in the monkey. The method requires calibration of the pharmacokinetic parameters of each monkey utilizing an intravenous bolus dose and assay of unchanged naltrexone levels in plasma as a function of time after dosing. Also required are periodic plasma levels of unchanged naltrexone obtained subsequent to administration of the delivery system. Release rates are then calculated as well as the total amount released. Application of the methodology to a biodegradable copolymer naltrexone delivery system in three monkeys showed an initial release rate of 3– 8% of the dose per day over the first 3– 5 days followed by a slow, rather constant release rate of 1– 3% per day from day 5 to the time of the last measurable plasma sample (36– 43 days). Comparison of alternative calculation methods using both experimental and simulated plasma naltrexone data verified the accuracy of the release rate calculations. The sum of the calculated total amount of naltrexone released plus the assayed amount remaining in the delivery system after removal from the animal accounted for 91– 94% of the administered dose in the two monkeys in which complete data were obtained.
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  • 113
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    Acta applicandae mathematicae 1 (1983), S. 105-120 
    ISSN: 1572-9036
    Keywords: Systems ; control ; Biomathematics ; identification in compartmental systems ; compartmental models ; pharmacokinetics ; optimal control of drugs
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract We first introduce some main problems in pharmacokinetics and then we propose methods for their resolution. Of course, identification problem is considered. A numerical efficient method is given. It brings back to the resolution of a succession of linear algebraic systems. In the case of non unicity we suggest an approach based on the adjunction of a criterion to minimize. The last part studies the optimal injection of a drug associated to an optimization criterion. An explicit solution can be found for a n-compartments linear system.
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  • 114
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    Investigational new drugs 1 (1983), S. 219-224 
    ISSN: 1573-0646
    Keywords: methyl-GAG ; rabbits ; pharmacokinetics ; three compartmental model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Using a paired ion exchange high pressure liquid Chromatographic assay, pharmacokinetic evaluation of methyl glyoxal bis guanylhydrazone (methyl-GAG) was performed in nine male New Zealand albino rabbits following administration of a single intravenous bolus dose of 50 mg/kg B.W (550 mg/m2 BSA). Blood samples were collected before and at intervals of 5, 10, 15, 30 min and 1, 2, 3, 4, 6, 8, 12, 18, and 24 h after administration of the drug. The analysis of experimental data indicates a three compartment open model with first order elimination from the central compartment described by the equation C pt =A.e−αt +B.e−βt +C.e−γt , where A, B, C, are 107.985, 4.785, and 0.763 μg/ml, respectively, α, β,γ, are 5.466, 0.487, and 0.030 h−1, respectively, and $$T_{\frac{1}{2}\alpha ,\beta ,\gamma } $$ are 7.6, 85.3 min and 23.1 h, respectively. The mean volume of distribution in the central compartment V c was 0.44 liters (l)/kg, volume of distribution Vd area 30.326 l/kg, and the total body clearance 0.9097 l/kg/h. The existence of a long terminal plasma half life of methyl-GAG reported previously in human studies was also confirmed in experimental animals and may explain the cumulative toxicity of this drug.
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  • 115
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1-15 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of this resin was examined by quantitative pyrolysis - gas chromatography. The decomposition does not follow the Hurd-Blunck mechanism generally obeyed by beta-hydrogen containing esters. Instead, phthalic anhydride is extruded almost quantitatively. It is proposed that the mechanism involves the rearrangement of the phthalate C—O bonds to extrude the anhydride, leaving a maleic acid - dipropylene glycol polyester chain.
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  • 116
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 31-39 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-grafted poly(p-phenylene terephthalamide)s (PPTA) were synthesized from PPTA and acrylonitrile or propylene oxide via metalation in a solution of the polymer in a sodium methylsulfinylcarbanion-dimethyl sulfoxide solvent at low temperatures. The introduction of these branches into the amide groups of PPTA increased solubility but decreased thermal stability. The effects of the branches on thermal properties and solubility are discussed. The structure of the graft copolymers is described on the basis of wide-angle x-ray diffraction, infrared spectra, and solubility.
    Additional Material: 6 Ill.
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  • 117
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 73-81 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of acrylonitrile initiated by a potassium superoxide (KO2)-nitrobenzene system was carried out in anhydrous dimethylsulfoxide (DMSO) at 25°C. The initial rate of polymerization was rapid and a high-molecular-weight polymer was obtained. The molecular weight was proportional to monomer concentration and inversely to concentration of initiator within 5 min. The overall activation energy was estimated as -2.6kcal/mol deg in the temperature range of 20-50°C. In addition to nitrobenzene anion radical, other anion radicals generated by one-electron transfer from KO2 to charge transfer agents such as m-dinitrobenzene benzoquinone, benzophenone, and naphthalene were effective in the polymerization of acrylonitrile. It is proposed that polymerization proceeds via an anionic mechanism that involves one-electron transfer from anion radicals to monomer.
    Additional Material: 7 Ill.
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  • 118
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 97-109 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diaryliodonium salts (I) undergo efficient thermal decomposition in the presence of copper (II) compounds. Such systems can be employed as a novel class of latent thermal initiators for cationic polymerization. An investigation of the mechanism of the reaction demonstrated that the copper (II) compound is first reduced to the corresponding copper (I) compound, which subsequently reduces the diaryliodonium salt. The cationic polymerization of some typical monomers using these new initiators was carried out to demonstrate the scope of their utility.
    Additional Material: 5 Ill.
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  • 119
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 147-154 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has been found that when hydrophobic monomers are polymerized in the presence of highly hydrophilic polymer seed particles, the second-stage hydrophobic polymers form cores surrounded by the first-stage hydrophilic polymers, resulting in “inverted” core-shell latexes. The formation of core-shell morphology by this inversion process has been found to be dependent on the hydrophilicity and molecular weight of the first-stage hydrophilic polymers and the extent of phase separation between the two polymers involved. Particle morphology has been examined by electron microscopy, surface acid titration, alkali swelling of particles, and surface reactivity.
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  • 120
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 155-163 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of polymeric microemulsions, viz. toluene/water/PS-PEO graft copolymer/2-propanol, has been studied by 1H-NMR spectroscopy. Results show that at low water contents, the copolymer adopts a rather diffuse micellar structure in which the rotational mobility of the ethylene oxide units is little affected by the ternary solvent mixture. Above a critical water concentration (ca. 4%), a restriction in mobility of the ethylene oxide chains is observed which has been related to the formation of an inverse micellar structure with water solubilized within the particles. The study of the chemical shifts and linewidths of water protons indicates that initially most of the water is hydrogen bonded to the hydrophilic part of the copolymer, then is present in its free form in water aggregates. These results confirm previous data obtained by dialysis equilibrium experiments.
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  • 121
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 751-760 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The concept of piezoelectric and pyroelectric effects in amorphous polymers is presented, with experimental results, details on sample preparation, and activity evaluation. Most evaluations were performed on 25-30 mol% tributyltin methacrylate/methyl methacrylate copolymers, which possessed good piezoelectric activity, antifouling properties, and paint-formulation characteristics. Solvent-induced orientation effects that lead to piezoelectric activity in amorphous, unpoled, polymers are also described.
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  • 122
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 737-750 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The physical state of the material obtained during the various stages of preparation of a typical MgCl2-supported, high-mileage propylene polymerization catalyst was studied by BET, mercury porosimetry, and x-ray diffraction techniques. The starting MgCl2 and the substance after HCl treatment have negligible BET surface areas. Mercury porosimetry showed that they have large pores with radii 〉 200 nm which are probably crevices between MgCl2 crystallites. The most pronounced physical changes occur during dry porcelain ball milling in the presence of ethyl benzoate. After 60 h or more of ball milling the material had a 5.1-7.3 m2 g-1 BET surface area, twice the pore surface area, and a smaller pore radius than before ball milling and a large reduction in crystallite sizes to almost ultimate dimensions. The crystallites were probably held together by complexation with ethyl benzoate in the form of large agglomerates. Subsequent reactions with p-cresol and triethyl aluminum had minor effects in further reduction of the MgCl2 crystallite size but efficiently brokeup the agglomerates. The final refluxing with TiCl4 increased the BET surface area to 110-150 m2 g-1 but may have increased the crystallite size somewhat due to cocrystallization of TiCl3 and AlCl3 with MgCl2. There may have been only 8-10 crystallites in each catalyst particle. The surface structure of the catalyst resembled those of the classical Ziegler-Natta γ-TiCl3·0.33 AlCl3 catalyst.
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  • 123
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 111-120 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of 4-aminophthalonitrile (APN) with 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BPTDA), and with 1,2,3,4-benzenetetracarboxylic dianhydride (PMDA) have been studied to optimize the conditions for the synthesis of monomeric thermosetting bisphthalonitrile compound. Suitable procedures for the synthesis of the two monomers are presented. Elemental analyses, IR spectra, dynamic thermogravimetric analyses, differential scanning calorimetry, 1H-NMR, and mass spectral studies have been used to characterize these compounds. Preliminary observations show that these materials can be polymerized to give high-temperature-resistant materials.
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  • 124
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 141-145 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article is a report of the investigation of the influence of monomer composition within optimum limits on the light-transmitting properties of MBS terpolymers obtained by the mass-suspension method. The high and nearly constant light-transmitting properties of the MS copolymer matrix have no effect on the light-transmitting properties of MBS with a MMA content up to about 20 mol % higher than that at the azeotropic point. The refractive index of the MS copolymers decreases uniformly as the mole ratio of MMA increases and becomes equal to the index of the SBR. Particle concentration in sizes up to 0.6μm increases as the MMA content increases to a given point at which the concentration remains constant as MMA continues to increase. The light-transmitting properties of MBS with a MMA content of 57 mol % are improved significantly. This fact is explained by a decrease in variation on the refractive index between the two phases to 0.0014 and by the increasing percentage of particles with sizes smaller than 0.6 μm up to 70%.
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  • 125
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 175-181 
    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 aromatic aldehydes and ketones could be reduced smoothly at room temperature by sodium dithionite using viologen derivatives as an electron transfer catalyst to obtain the corresponding alcohols in good yields. Viologens (methyl viologen and polymer) acted catalytically and active species in the reduction were quinoid forms which were obtained by two-electron reduction of viologens.
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  • 126
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 953-960 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For a fundamental study of the electrochemical behavior of electroactive polymers a series of poly(3-vinyl-10-methylphenothiazine) (polyMPT), copolymers of 3-vinyl-10-methylphenothiazine and methyl methacrylate (MMA) (copolyMPT), and 3-ethyl-10-methylphenothiazine (EMPT) (a related monomer model) were prepared. The methylphenothiazine groups in these compounds showed reversible, one-electron oxidation waves in the triangular-were voltammograms. From a detailed comparison of the voltammograms between these polymers and EMPT it was revealed that the electroactive groups in poly MPT were not the “noninteracting” centers in the strict sense, whereas those in copolyMPT, in which the centers are spaced with the MMA segments, were typically noninteracting in nature; that is, in polyMPT the oxidation takes place at the potential 40 m V lower than that of EMPT and copolyMPT exhibited a wave identical to that of EMPT in shape and potential. The exhaustive electron transfer occurred from polyMPT to the electrode. On the other hand, a significant number of centers remained unoxidized in copolyMPT. The self-exchange electron transfer within the polymer coil facilitates the exhaustive oxidation. For this event the proximity of the centers was an essential factor.
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  • 127
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 969-983 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Substantial hole transport can be achieved in organic polymers simply by incorporating aromatic amine groups into the monomer. Hole mobilities similar to or greater than those in poly(N-vinyl-carbazole) (PVK) were measured in a series of high molecular weight arylamine-substituted polymethacrylates. The hole transport in these polymers is electric-field-dependent as in PVK, varying between E and E2 within a range of 4 × 104 - ∼9 × 105 V/cm. The polymers also exhibit carrier generation in ultraviolet (UV) light in the range of absorption. Synthesis of the monomers, their polymerization, and the general properties of these polymers are discussed.
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  • 128
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1025-1032 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermally stable poly(metal phthalocyanine)imide copolymers were prepared with metal(11) 4,4′,4″,4‴ -phthalocyanine tetraamines, 4,4′ -diamino diphenyl ether, and 3,3′,4,4′ -benzophenone tetracarboxylic dianhydride. Variables such as molar concentrations of the reagents, solvents, and temperature were investigated to optimize the conditions of the polymerization. Inherent viscosity, and infrared (IR) spectral and thermogravimetric analysis (TGA) studies were done to characterize the polymers. These polymers are stable and thier decomposition temperatures both in air and nitrogen are greater than 500°C. Their char yields at 800°C in nitrogen varied between 60 and 76%, depending on the type and concentrations of the metal phthalocyanine tetraamines. These polymers can be used to produce heat-stable films, fibers, varnishes, and adhesives.
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  • 129
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 923-936 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of the reaction conditions (time, temperature, concentrations of the monomer, and the initiator) on the amount and composition of the oligomers and high molecular products formed during the heterogeneous anionic polymerization of ∊-caprolactone was investigated. The polymerization was initiated by KC24 in xylene or tetrahydrofuran. Conditions were found under which intra- and intermolecular transesterification was strongly suppressed, thus providing the opportunity for the formation of polyesters with viscometric molecular masses of more than 300,000 and good yields (80% and higher). The total quantity of products with a viscometric molecular mass below 2500 did not exceed 15%; that of the cyclic dimer was not in excess of 5%. Peculiar features of the KC24 initiated polymerization are the insignificant rise in the number of oligomers and the formation of high polymers even in strongly diluted solutions of ∊-caprolactone (0.2 mol/L and lower). The quantity and molecular mass of the polymers obtained decreased as the temperature increased. It was also established that the polymerization of the cyclic dimer of ∊-caprolactone is not initiated by KC24.
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  • 130
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1151-1157 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyaromatic either-sulfone-ketones containing fluoro-substituted p-cyclophane units were prepared from isophthaloyl chloride, terephthaloyl chloride, diphenyl ether, diphenoxydiphenyl sulfone, and a small amount of 1,1,2,2,9,9,10,10-octafluoro-[2,2]-p-cyclophane (type A) or pseudo-p-1,12,2,9,9,10,10-octafluoro-[2,2]-p-cyclophane bis-acid chloride (type B) by Friedel-Crafts-type polymerization. The p-cyclophane units were incorporated as crosslinking sites. Crosslinking was achieved by curing polymers at 300-350°C for several days. The polymers obtained, containing 1-10 wt % fluoro-substituted p-cyclophane units, were moderately soluble in dichloromethane, DMF, and sulfuric acid with inherent viscosities between 0.4 and 0.6. Laminates on glass fiber were made with excellent thermal stability.
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  • 131
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1289-1303 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The esterification of the carboxyl group in copoly(γ-benzyl-L-glutamyl-L-glutamic acid) was carried out using N-hydroxysuccinimide and dicyclohexylcarbodimide to yield the activated site for the coupling reaction with amino compounds. The α-helix stability of the reactive copolymer thus obtained is remarkably affected in the presence of succinimide ring. This copolymer was proved to react nearly completely with amino alcohols such as 2-aminoethanol, 3-aminopropanol, and diethanolamine. The copoly(N5-hydroxyalkyl-L-glutamine) thus prepared is insoluble in water, since the benzyl ester remains in this copolymer. The copoly(α-amino acids) having another functional group were also prepared using aminoalkylsilane. Crosslinked poly(α-amino acids) were prepared by the reaction of the reactive copolymer with a low-molecular-weight polymer of PBLG having one amino group on each end of its main chain which was obtained from the corresponding NCA using p-diaminobenzene as an initiator. Another crosslinked polymer was prepared using an alkyl diamine such as 1,6-diaminohexane or 1,12-diaminododecane as a crosslinking reagent. The crosslinked copoly(α-amino acids) bearing the activated site are able to further react with various compounds having amino groups.
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  • 132
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1417-1422 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reversible isomerization of poly(chloromethylthiirane) and poly(3-chlorothietane) represents a new kind of polymer reaction and a new method of copolymer synthesis. In chloroform, in dichloromethane, or in nitrobenzene the reaction is well described by reversible first-order kinetics. A rate increase of ca. 40% on changing the solvent from chloroform to nitrobenzene is consistent with an isomerization mechanism that involves a rate-determining attack of the backbone sulfur atom on the neighboring carbon-chlorine bond and rapid ring-opening of the thiiranium ion intermediate by chloride ion.
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  • 133
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 609-613 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 134
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 633-634 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 135
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1819-1829 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed magic angle spinning 13C-NMR investigation of the intractable polymer prepared by plasma polymerization of toluene and isotopically labeled toluene led to a proposed model for the structure of the polymer and suggested some of the likely processes that occur in the gas phase leading to film formation. From the 13C spectra four resolved resonances permitted the determination of the contribution of nonprotonated and protonated unsaturated as well as methyl and other aliphatic carbons to the polymer structure. Specific 13C isotopic labeling of the methyl and phenyl C-1 toluene carbons in the injected liquid vapor allowed the destination of these carbons in the deposited polymer to be traced. The dominant structure is derived primarily from two precursors: benzyl radical and toluene itself. The 13C data further requires a net saturation of ca. 30% of the toluene double bonds and a net displacement of hydrogen by carbon on ca. 20% of the toluene ring carbons.
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  • 136
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 803-810 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The free radical polymerization of acrylonitrile (AN) initiated by Cu(II) 4-anilino 2-one [Cu(II) ANIPO] Cu(II), 4-p-toluedeno 3-pentene 2-one [Cu(II) TPO], and Cu(II) 4-p-nitroanilino 3-pentene 2-one [Cu(II) NAPO] was studied in benzene at 50 and 60°C and in carbon tetrachloride (CCl4), dimethyl sulfoxide (DMSO), and methanol (MeOH) at 60°C. Although the polymerization proceeded in a heterogeneous phase, it followed the kinetics of a homogeneous process. The monomer exponents were ≥2 at two different temperatures and in different solvents. The square-root dependence of Rp on initiator concentration and higher monomer exponents accounted for a 1:2 complex formation between the chelate and monomer. The complex formation was shown by ultraviolet (UV) study. The activation energies, kinetics, and chain transfer constants were also evaluated.
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  • 137
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    Topics: Chemistry and Pharmacology
    Notes: N-Methylacrylamide (NMAAm) was polymerized quantitatively by using di-tert-butyl peroxide as photosensitizer to be, for the most part, incorporated in living poly(NMAAm) radical. The living polymer radical reacted effectively with acrylate monomers to yield block copolymer. Longer alkyl chain of the acrylate monomer caused a decrease in the conversion of the second monomer. Methacrylate monomers, such as methyl methacrylate and cyclohexyl methacrylate, showed relatively low reactivities in comparison with acrylates. Styrene exhibited a much lower conversion. The resulting block copolymers showed different thermochromic behaviors in methyl benzoate from that of poly(NMAAm). This is explained on the basis of the difference between refractive indexes of the block copolymers and poly(NMAAm).
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  • 138
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 865-881 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyimide films based on either 3, 3′, 4, 4′-benzophenone tetracarboxylic acid dianhydride or pyromellitic dianhydride with 4,4′-oxydianiline have been doped with copper(I) and copper(II) complexes. High-quality, flexible, glass-cast films have been obtained which exhibit increased softening temperatures and lower polymer decomposition temperatures. The atmosphere and glass sides of the films are quite different. The copper(I) dopant is oxidized on the air side of the film, while the glass side contains predominantly copper (I). In the copper(II) case most of the copper appears on the air side as a silvery substance in the Cu(II) state. Chemical as well as ion etching can remove this material. Electrical resistivity of the copper(II)-doped films is decreased by three to five orders of magnitude relative to the polymer alone.
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  • 139
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 883-890 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of two phenylated bifunctional monomers, dimethyl 4-(4-(p-aminophenoxy)phenyl)-3,5,6-triphenylphthalate and dimethyl 4-(4-(4-(p-aminophenoxy)phenoxy)phenyl)-3,5,6-triphenylphthlate, was accomplished. Polymerization in solution or by a bulk polymerization procedure yielded a series of low molecular weight phenylated polyimides. The polymers were soluble in chlorinated hydrocarbons and exhibited thermal stabilities comparable to other polyimide systems.
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  • 140
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 937-941 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structural changes in the potassium graphitide KC24 in its interaction with ∊-caprolactone, γ-butyrolactone and pivalolactone are examined by profilometric measurement and electron scanning microscopy. The interaction of KC24 with a nonpolymerizable lactone-γ-butyrolactone proceeds without delamination of the graphitide. The polymerization of ∊-caprolactone and pivalactone in the interlayer spaces of KC24 leads to destruction of the initiators structure. An increase in the temperature and monomer concentration enhances the delamination of the graphitide.
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  • 141
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure was developed by which polymer colloids can be prepared by polymerizing aerosol droplets of monomers with an initiator in the vapor state. This work describes the formation of poly(p-tertiarybutylstyrene) particles by exposing the corresponding monomer droplets to trifluoromethanesulfonic acid. It was found that the monomer-to-initiator mass ratio is the critical factor in determining the uniformity and morphology of the particles. Under ideal conditions spheres of narrow size distribution are obtained. Otherwise porous particles or soft particles with whiskers may develop. The aerosol was prepared in a falling film generator, but other procedures for producing monomer droplets may be used.
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  • 142
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 999-1012 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polycondensation of the diacid chloride of 2-(3-carboxy vinyl)phenyl-1,3-dioxoisoindoline-5-carboxylic acid with m-phenylenediamine and the diacid chloride of 2-(4-carboxy phenyl)-1,3-dioxoisoindoline-5-carboxylic acid with 1,5-bis(3-aminophenyl)1,4-pentadien-3-one was carried out in polar solvents to produce new unsaturated polyamide-imides. The solution and the thermal, electrical, and a few other properties of the polymers were studies. The polymers were soluble in highly polar solvents. The solubility parameter of the polymers was calculated from the Small's group contribution. The polymers were fairly thermostable and underwent crosslinking creaction when heated, preferably in the presence of a suitable catalyst. The crosslinked polymers were in soluble even in highly polar solvents and possessed higher thermal stability. The swelling behavior of the polymers was studied and the molecular weight between two consecutive crosslinks was determined. X-ray diffraction and the dielectric properties of the polymers and their crosslinked products were also studied.
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  • 143
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1013-1024 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crosslinked polystyrene particles were prepared by Friedel-Crafts suspension crosslinking of polystyrene using 2,4-dichloromethyl-2,5-dimethyl benzene as crosslinking agent. The polymer was dissolved in nitrobenzene and reaction occurred in a 70 wt % aqueous solution of ZnCl2 with poly(vinyl alcohol) as a suspending agent. The spherical particles produced were swollen in toluene, chloroform, and tetrahydrofuran to determine their equilbrium polystyrene volume fraction. Analysis of the crosslinked macromolecular structure gave values of number-average molecular weight between crosslinks of M̄c = 900-5900 increasing as the nominal crosslinking ratio X decreased from 0.75 to 0.0625 mol of crosslinking agent per mole of polystyrene repeating unit. Porosimetric analysis contributed to the understanding of the importance of the pore structure for swelling behavior.
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  • 144
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An efficient kinetic method of reactivity ratio measurement for binary copolymerization of gaseous monomers4 that does not require the measurement of copolymer composition and can be applied to the data obtained in a single copolymerization run was modified and applied to olefin copolymerization with heterogeneous Ziegler-Natta catalysts. Estimated r1 and r2 values for pairs like ethylene-propylene and propylene-1-butene agree favorably with published data.
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  • 145
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1097-1110 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new redox couple based on the copper-catalyzed reduction of diaryliodonium salts with benzoins has been used to initiate cationic polymerizations of cyclic ethers and esters. A proposed mechanism for initiation by this redox couple is based on its stoichiometry and on the nature of the products. It was concluded that initiation of polymerization occurs both by direct arylation of the monomer and by protonation by strong Brønsted acids. The polymerization of several typical cationically polymerizable monomers using this new redox initiator were studied.
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  • 146
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1125-1137 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A regenerable dihydronicotinamide immobilized on a macroreticular polystyrene carrier was developed and used in an aqueous medium for the reduction of trifluoroacetophenone to the corresponding alcohol. It was shown that the second-order rate constant for the polymer-bound reagent is significantly lower than that of the low-molecular-weight analog 1-benzyldihydronicotinamide. The observed reaction rate, however, was of the same order of magnitude as that due to enrichment of substrate in the polymeric pores. It was possible to depress the undesired side reactions to 10-15% per reaction cycle, thereby allowing reutilization of the functionalized polymer.
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  • 147
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2451-2461 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 337.1-nm emission of a pulsed nitrogen laser was shown to initiate the crosslinking polymerization of epoxy-acrylate photoresists effectively. We evaluated the extent of curing from the amount of insoluble polymer formed and by the decrease in infrared (IR) absorption of the reactive double bond at 810 cm-1. With the large power density available in the laser pulse (0.5 MW cm-2) rates of polymerization as high as 108 mol L-1 s-1 were observed in the presence of air. Quantum yield measurements indicated that each photon absorbed can create as many as 450 crosslinks; the kinetic chain length was calculated as ca. 4000 double bonds polymerized per initiating radical. During the induction period due to oxygen inhibition each photoinitiator radical consumed 1 O2 molecule. The influence of the monomer and photoinitiator used on the sensitivity of the resin was examined; the best performing formulation contained the epoxy-acrylate oligomer, pentaerythritol triacrylate, as monomer and 2,2 dimethoxy-2-phenyl-acetophenone as photoiniatior. All the formulations studied can be cured by a single 500-kW laser pulse of 8 ns duration, provided that the irradiation is carried out in an inert atmosphere or with a focused laser beam.
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  • 148
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2491-2501 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Values calculated for the activation volume for chain propagation, ΔV
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  • 149
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2529-2534 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article reports a study of the catalytic addition reaction of ferrocene containing dihydrosilane to diacetylenic silicon derivatives. A hypothetical structure based on reaction kinetics and spectral data is presented. The oligomers obtained were studied by TG and DTA from ambient temperature to 1000°C in oxygen atmosphere (80 mL/min). The existance of phenyl groups in the structure of the oligomers makes them less stable than those with derivatives.
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  • 150
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1195-1201 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Our previous NMR investigations of chemically crosslinked polypropylene (PP) were focused mainly on testing the relation between NMR relaxation times as a function of crosslinking compound concentrations and the influence of structural factors found by this method on mechanical and other properties of this polymer.1,2 In these investigations, however, we did not consider the state of mobility of any part of the polypropylene chain under the influence of the network; therefore in this article we have attempted a clarification of this problem.
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  • 151
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1233-1237 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 6 Ill.
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  • 152
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1241-1249 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New polyphthalimidine-forming monomers, 5,5′-(oxydi-p-phenylenedicarbonyl)bis(3-benzylidenephthalide) and the 6,6′-derivative, were synthesized by the Friedel-Crafts reaction of diphenyl ether with 5- and 6-chloroformyl-3-benzylidenephthalide, respectively. The direct polycondensation of these bisphthalides with both aliphatic and aromatic diamines in o-phenylphenol at 200-250°C afforded polyphthalimidines having inherent viscosities of 0.2-1.2 dL/g in almost quantitative yields. Syntheses of aliphatic polyphthalimidines with higher inherent viscosities were also achieved by a two-step procedure involving ring-opening polyaddition and subsequent thermal cyclodehydration. All the polymers were amorphous and readily soluble in N-methyl-2-pyrrolidone (NMP), m-cresol, nitrobenzene, pyridine, and chloroform. Tough and flexible films could be cast from NMP solutions of the polymers. Glass transition temperatures of the polyphthalimidines were in the range of 158-246°C. The thermogravimetry of the aromatic polymers showed 10% weight loss in air and nitrogen at 445-515 and 500-520°C, respectively. The crosslinking reaction of some benzylidenependant polyphthalimidines took place at 300°C through double-bond addition to afford cured polymers with improved thermal stability.
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  • 153
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2617-2628 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Although polymerization of 2,5-dibromothiophene via coupling of the Grignard reagent with organonickel salts was reported in two earlier communications, a detailed examination of reaction variables was not done. This report provides results from variation in the following: time, amount of magnesium, amount of iodine, dilution, and variation in the halide of the monomer. The highest yield was obtained for reactions with 1:1 molar ratio of monomer to magnesium in more concentrated solutions of tetrahydrofuran for a reaction time of 4 h. For variation in the halogen of the monomer the following yield sequence was obtained: I 〉 Br 〉 Cl. The results are compared with the corresponding benzenoid system investigated by Yamamoto. In addition, polymerization studies were carried out with other brominated thiophene monomers. Use of an organic promoter (cis-1,4-dichloro-2-butene) in place of a nickel salt proved successful in the generation of poly(2,5-thienylene).
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  • 154
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1371-1384 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Flash photolysis of copper (II)-bis(amino acid) complexes (amino acids: glutamic acid, serine, or valine) in deaerated aqueous solution produces transient species having absorption maxima at around 350 nm. The transient species are identified as copper (II)-alkyl complexes. In the case of Cu(valine)2 at pH 〉 6.5 formation of Cu(II)-alkyl complex is not observed; this is interpreted to be due to the presence of two bulky methyl groups of the coordinated valine ligand, which hinders the rearrangement. Pseudo-first-order rate constants for the decay of the transients are determined at different pH with varying concentration of amino acid ligand. The free-radical species of the complexes responsible for the initiation of the vinyl polymerization reactions are identified as Cu(I)-coordinated amino acid radicals which are formed in the primary photochemical reaction of the complex. A mechanism for the secondary reactions involving the initiating species consistent with the nature of the product formed and the pH dependence of the decay of the transients is proposed.
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  • 155
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1401-1416 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The results of studying the radiation curing of methacryloyloxyalkyl carbonates (MC), a new type of oligomer, are presented. These oligomers are notable for their high rates of radiation curing. The radiation yield G(-M) is 2 × 105 for MC and 2 × 104 for triethylene glycol dimethyacrylate. The polymerization rate of MC appeared to be proportional, independent of the conversion degree, to the irradiation dose rate in the power of 0.9-1.0 (for dose rates ranging from 0.4 to 15 rad/s). In regard to the temperature dependence of the polymerization rate of MC for small conversion degrees, two temperature regions with different values of effective activation energy (18-20 kcal/mol and 2 kcal/mol, respectively) were observed. When an irradiated MC sample is being unfrozen, its polymerization occus in the region of devitrification (220-240°K). As distinct from mass polymerization, in the polymerization of MC solutions in acetone and benzol the mobility of growing chains increases so that the bimolecular termination becomes possible and the limiting conversion of double bonds is derived. Rather small irradiation doses necessary for curing MC and the proportionality of the radiation-induced polymerization rate to the dose rate make these oligomers valuable for various industrial applications.
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  • 156
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1445-1455 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The amount of in-cage and out-of-cage recombination of initiator radicals has been measured by recovering the recombination products of simultaneous decomposition of an unlabeled and a deuterium-labeled initiator. The occurrence of recombination products generated from both an unlabeled and a deuterium-labeled initiator fragment, which can be monitored in a mass spectrometer, indicate out-of-cage recombination. It turned out that in the course of decomposition of dibenzoylperoxide in benzene, biphenyl was not produced by direct recombination of the phenyl radicals originally generated, but rather by interaction with benzene. Upon decomposing azoisobutyronitrile in various solvents, however, both in-cage recombination and out-of-cage recombination were observed. When small amounts of styrene were added to such systems, the initiator radicals tended rather to react with styrene than to undergo out-of-cage recombination.
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  • 157
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3033-3033 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 158
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3035-3040 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free-standing polyphenylene films, prepared by the electrochemical oxidation of benzene in an HF-benzene, two-phase system, were investigated. From electron microscope pictures, x-ray diffraction patterns, and infrared (IR) spectra of polyphenylene films and commercial polyphenylene powder it is concluded that the films, which are largely para linked, contain in addition a substantial amount of meta and possibly ortho linkages and are amorphous in nature. Doping with AsF5 increases the electrical conductivity of the otherwise insulating films to 10-4-10-2ohm-1cm-1; doped films are relatively stable in air. The lower conductivity of doped films with respect to reported values for chemically synthesized poly-p-phenylene appears to be the result of the amorphous nature of the films.
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  • 159
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3041-3053 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(vinyl acetate) was graft-copolymerized onto casein in the presence of potassium peroxydisulfate-ascorbic acid. The effect of synthetic variables on the rates of conversion of monomer (Rp), graft copolymerization (Rg), and homopolymerization (Rh), percent grafting, and grafting efficiency were investigated and the results, compared with the system initiated by peroxydisulfate alone.
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  • 160
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3073-3082 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title diacetylenic compound (D3) and its derivatives dibenzoate (D3B), dinitrobenzoate (D3mNB), ditosylate (D3PTS), and diurethane (D3PU) were synthesized and their solid-state reactivity examined under irradiation and thermal stimulation. D3, D3B, and D3PTS crystallized in reactive phases. The thermal and irradiation polymerization behavior of D3 and D3B was examined further by time-conversion curves.
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  • 161
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3115-3127 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this article we report the synthesis of a polyurea containing the chelating ligand bipyridine and concentrate on some of the catalytic properties of its palladium complexes.
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  • 162
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3145-3153 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ionene polymers characterized by the alternating structure of ionene and crystalline poly(ethylene oxide) (PEO) segments were prepared as a function of PEO segment size. A microstructure of these ionenes and their 7,7,8,8-tetracyanoquinodimethane (TCNQ) salts were investigated with x-ray diffraction patterns, thermal scanning behavior, and polarizing micrographs. On the basis of this microstructure, the change in resistivity with temperature was studied. In Arrhenius' plots of the resistivity the simple salts in which the spherulites consisting of the PEO segments were observed showed a sharp decrease in resistivity with a rise in temperature [critical temperature resistor (CTR)] at about the melting point of the PEO segments, whereas the other simple salts in which the spherulites were not observed showed linear temperature dependence. The switching properties were confirmed similarly in repetitive heating/cooling cycles. This CTR characteristic was attributed to an increase in continuity in the conduction paths by melting spherulites. The apparent switching properties were not observed in the complex salts.
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  • 163
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3191-3199 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethylene glycol bis(methyl fumarate) (EGBMF) was prepared as a new type of divinyl compound and reactive oligomer: a needle crystal, m.p. 104.5°C. Homopolymerization of EGBMF was carried out in dioxane with 0.1 mol/L AIBN at [M] = 1 mol/L and 60°C; the rate of polymerization was estimated to be 4.44 × 10-6 mol/L s in a good agreement with diethyl fumarate (DEF). The cyclization constant Kc was obtained as 1.64 mol/L, being rather low compared with diallyl oxalate which is 1,9-diene having two ester groups analogous to EGBMF. Gelatin occurred at about 35% conversion. Finally, the copolymerization of EGBMF (M1) with diallyl phthalate (DAP) (M2) is tentatively explored with the intention of the improvement of allyl resins in mechanical properties; remarkable rate enhancement was observed for copolymerization. The monomer reactivity ratios were estimated to be r1 = 0.96 and r2 = 0.025, the r1 value being reduced compared with the DEF-DAP copolymerization system. These results are discussed from the standpoint of steric effect on the polymerization of fumarate as an internal olefin.
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  • 164
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3233-3239 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Arylsulfonyl chlorides were successfully used as a new condensing agent for the synthesis of polyaryl esters by the direct polycondensation of aromatic dicarboxylic acids and bisphenols. High-molecular-weight polymers (Mw = 84,000) were prepared by reacting dicarboxylic acids with the sulfonyl chlorides in pyridine in the presence of LiCI, followed by treating with a pyridine solution of bisphenols. The polycondensation was significantly affected by factors, such as, the kind of arylsulfonyl chlorides, its amount, the conditions of initial reaction of the acids with the sulfonyl chlorides, the amounts of LiCI added, and dropwise addition of bisphenols.
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  • 165
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3337-3340 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 166
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3353-3360 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Following a series of experiments on the effect of different factors of the electrical conductivity of carbon-black-loaded styrene butadiene rubber, an attempt was made to study the effect on electrical conduction of changing the sulfur content. It was found that an optimum sulfur content leads to a swelling-resistant composite with good electrical insulation. This was done for dry as well as wet specimens of rubber.
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  • 167
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3381-3388 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The initiation of polymerization of vinyl monomers such as methyl methacrylate (MMA) and methyl acrylate (MA) by a charge transfer complex formed between n-butylamine(nBA) and carbon tetrachloride (CCl4) in dimethylsulfoxide (DMSO) at 30°C is slow. The effect of the dimethylsulfoxide complexes of Rh(III) and Ru(II) on the polymerization of MMA and MA in the presence of nBA, and CCl4 in DMSO has been studied. The rate of polymerization and percent conversion of the MMA and MA at 30°C are evaluated at the critical concentration of the metal complexes. At the critical range of the metal complex concentrations, both Rp, and percent conversion of MMA and MA were found to be highest. However, above and below the critical concentrations, Rp and percent conversion of the monomers were found to decrease. A suitable mechanism for the polymerization has been proposed.
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  • 168
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3403-3424 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Nitro-N-vinylphthalimide (4) was synthesized by two different procedures. Compound 4 was not polymerizable or copolymerizable by AIBN. Poly(N-vinylphthalimide) (17) was prepared and partially nitrated at 10-25°C. N,N′-(1,2-Ethanediyl)bis(4-nitrophthalimide) (15) and N,N′-(1,3-propanediyl)bis(4-nitrophthalimide) (16) were prepared by the condensation of the corresponding diamine with phthalic anhydride followed by nitration of the condensation products. 4-Nitrophthalic anhydride was prepared by the hydrolysis of 15. Four styrene-substituted phthalimide monomers were synthesized. These include N-(4-vinylphenyl)phthalimide (25a), N-(4-vinylphenyl)-3-fluorophthalimide (25b), N-(4-vinylphenyl)-3-nitrophthalimide (25c), and N-(4-vinylphenyl)-4-nitrophthalimide (25d). Monomers 25a and 25b were polymerized by freeradical initiator (AIBN), whereas monomers 25c and 25d were not polymerizable or copolymerizable by AIBN due to a strong inhibitive effect exerted by the nitrophthalimide group. Monomers 25c and 25d were cationically polymerized (BF3·OEt2). Monomer 25b and styrene were copolymerized and their reactivity ratios were r1 = 1.7 and r2 = 0.55, respectively. The prepared polymers are useful as backbone polymers for grafting living anionic polymers.
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  • 169
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3453-3477 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolysis of polyacetylene is marked by high yields of proton-enriched products methane, ethane, ethylene, propane, polypylene, butadiene, cyclopentadiene, 1,3-pentadiene, and toluene in total amounts exceeding benzene. The activation energies for their formation are low. Polyacetylene doped with AsF5 and iodine produced these products in even higher yields of two to 17 times of undoped polymers. The dominant mechanism is thought to be random-chain scission followed by electron-proton exchange reactions. Polymethylacetylene is thermally less stable than polyacetylene. Pyrolysis gave mesitylene as the expected main product. However, as in the case of polyacetylene, large amounts of proton-enriched products were formed with moderate activation energies. (The yields of methane, propylene, and propane are nearly the same in the pyrolysis of polymethylacetylene as compared to that of polyacetylene at 923°K referenced to mesitylene and benzene, respectively.) By analogy, mechanisms involving both electron-proton and electron-methyl exchange reactions were proposed to account for the formation of all the pyrolyzates of polymethylacetylene. These reactions, not observed in the pyrolysis of polypropylene and polyisoprene, are attributable to the conjugated backbone permitting facile migrations of electrons, protons, and methyl groups.
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  • 170
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acrylic anhydride (AAn) and methacrylic anhydride (MAAn) were polymerized with radical initiator in polar solvents at high temperatures. The polymers obtained were found to consist of five-and six-membered ring structures by comparing IR spectra of the polymers with those of model compounds, succinic anhydride, and glutaric anhydride. Hydrolysis and methylation of the polymers gave new polymers composed of head-to-head (HH) and head-to-tail (HT) methyl acrylate (MA) or methyl methacrylate (MMA) units. The content of HH unit of these HH/HT polymers was determined by 1H-NMR and 13C-NMR spectra. The softening, glass transition, and thermal degradation temperatures of the poly(MA) with HH and HT units were found to somewhat increase with increasing of the content of the HH units. On the other hand, the glass transition and thermal degradation temperatures of the poly(MMA) with HH and HT units increased similarly, but the softening temperature decreased as the content of the HH units increased.
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  • 171
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3563-3571 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article describes a technique for the homogeneous lithiation and subsequent carboxylation of high-molecular-weight polystyrenes containing up to 14 mol % p-bromostyrene. Thus, poly(styrene-co-p-bromostyrene)s were reacted in dilute tetrahydrofuran solution with large stoichiometric excesses of n-butyllithium with no precipitation of ionomer and subsequently carboxylated with anhydrous carbon dioxide or dry ice. By this technique polystyrenes in which up to 100% of the original bromine groups had been replaced by carboxyl functionalities were obtained.
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  • 172
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crosslinked polystyrene beads which immobilized two terminal azophenoxide groups of an azobenzene-crown(24-crown-8)-azobenzene unit were synthesized. The polymer beads adsorbed Cs+ in the dark while they rapidly released Cs+ into the solution under UV-light irradiation, and the photoresponsive complexation occurred reversibly. On the other hand, the crosslinked polystyrene beads which immobilized one terminal azophenoxide group of an azobenzene-crown (24-crown-8) unit scarcely (or only to a smaller extent) exhibited such a photoresponsive behavior. Similarly, the polymer beads which immobilized two terminal azophenoxide groups of an azobenzene-crown (18-crown-6) azobenzene unit reversibly adsorbed and desorbed K+ in response to UV-light irradiation. The novel photoresponsive behavior is ascribed to a conformational distortion of the crown rings which induced by the photoisomerization of the azobenzene moiety, although the photoinduced polarity change of the polymer beads is not completely ruled out. The results suggest that the polymer support is useful as a “fixed point” to enforce the conformational changes of immobilized functional molecules.
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  • 173
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3597-3600 
    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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  • 174
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3573-3590 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel aromatic-telechelic polyisobutylenes were prepared and characterized: α,ω-diphenylpolyisobutylene, α-phenyl-ω-tolylpolyisobutylene, and α,ωditolylpolyisobutylene. The syntheses involved the preparation of asymmetric telechelic prepolymers (α-phenyl-ω-tert-chloropolyisobutylene and α-tolyl-ω-tert-chloropolyisobutylene) by the minifer method and quantitative alkylation of benzene and toluene by the prepolymer. The terminal aromatic rings of these telechelic polyisobutylenes were quantitatively nitrated, acetylated, and chlorosulfonated and a series of further novel telechelic products was obtained. Characterization of these derivatives provided additional proof for the telechelic structure of the starting prepolymers. The quantitative reduction of nitroaryl-telechelic polyisobutylene by SnCl2/HCl led to aminoaryl-telechelic polyisobutylene which was used to cure bisphenol-A diglycidyl ether. These new flexible epoxy networks exhibited outstanding heat and hydrolytic stability combined with satisfactory mechanical properties.
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  • 175
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1997-2001 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thyroxine methyl ester amides of mono-, di-, and tri-glycyl methacrylates have been prepared. Water-soluble polymers formed from thyroxine methacrylate monomers by free-radical copolymerization with acrylamide had molecular weights of (2-4) × 104 (by viscometry). A fluorescent polymer was prepared by copolymerization with a fluorescein methacrylate monomer. Similarly, a polymeric thyroxine material was prepared with amine functionality by copolymerization with N-3-aminopropylmethacrylamide. These polymers may have interesting biological and immunochemical properties.
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  • 176
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2177-2188 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal and thermo-oxidative degradation of poly(vinyl chloride)s (PVCs) containing increased concentrations of allylic chlorines, PVC(A)s, prepared by controlled chemical dehydrochlorination with potassium-t-butoxide (t-BuOK) have been studied. The introduction of small amounts of internal allylic chlorines into PVC significantly decreases the thermal and thermo-oxidative stability of the resin. A linear relationship exists between the initial rates (VHCl)0 of thermal and thermooxidative dehydrochlorination of solid PVC(A)s and the concentration S of internal allylic chlorines. Both the slope and the intercept of the thermo-oxidative (VHCl)0 vs. S plot are higher in oxygen than those obtained in nitrogen at the same temperature; this finding is attributed to fast oxidation of polyenes, and to peroxy radicals formed during polyene oxidation, which initiate subsequent HCl loss by attacking normal repeat units in PVC. The extent of HCl loss as a function of time during thermal degradation of PVC(A)s in intert solvent shows a rapid initial phase followed by a slower stationary phase. The first phase is due to dehydrochlorination involving the labile chlorines, while the stationary phase indicates random initiation of HCl loss at normal—CH2—CHCl— repeat units. Initial rates of HCl loss increase with S, while the rates of HCl loss during the stationary phase are independent of S. The rate constant of initiation of HCl loss at internal allylic chlorines is almost four orders of magnitude higher than that of random initiation; however, the former is still orders of magnitude lower than that of chain propagation. Quantitative analysis of UV-visible spectra of PVC(A)s degraded in solution suggests geometric polyene distribution. The average length of polyenes decreases as the extent of HCl loss increases and reaches a constant value of ca. 3 at ca. 1% HCl loss for all the investigated PVC(A) samples.
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  • 177
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2237-2240 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of monodisperse polystyrene substituted with single dimethylamino groups is described. Three methods are adopted. The first involves the use of a dimethylamino-substituted initiator to give an end amino group. The second uses an ester coupling reaction with a dimethylamino-substituted methyl valeric ester to give a central amino substituent. The third method, which is capable of giving an amino substituent at any selected place along the chain, uses a dimethyl-amino-substituted butadiene derivative as a comonomer in a sequential polymerization. This latter method takes advantage of the unusual reactivity ratios of styrene and dienes in anionic copolymerization.
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  • 178
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2249-2259 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two copolymers composed of p-hydroxybenzoate (PHB) and biphenylene terephthalate (BPT) with PHB/BPT ratios of 1/2 and 2/1 were characterized with respect to their tendency to exhibit liquid-crystalline behavior in the melt phase. The BPT -rich copolyester, PHB/BPT = 1/2, displayed a birefringent melt phase of very high viscosity and no tendency to crystallize on cooling. The resulting fused material exhibited what apeared to be a second-order transition at 170°C. The PHB-rich composition, PHB/BPT = 2/1, also exhibited a highly birefringent melt phase of high viscosity which was quite shear sensitive. This polymer melt had little tendency to crystallize on cooling; however, on reheating no apparent second-order transition could be detected. The observed phase changes were characterized by differential scanning calorimetry, hot-stage microscopy, and wide-angle x-ray diffraction techniques. Additional data, pertaining to the compositional nature and apparent sequence distribution, were obtained by 13C-NMR spectroscopy of the solid materials through magic-angle spinning, dipolar decoupling, and cross-polarization techniques.
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2277-2281 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyesters were synthesized from the dichlorides of 2,5-dimethoxyterephthalic and 2,5-dimethoxy-1,4-benzenediacetic with dialcohols. The polymers were characterized by elemental analysis and infrared (IR) spectroscopy. Their intrinsic viscosity, glass transition temperature, and thermal decomposition were determined.
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  • 180
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2301-2309 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ten polyfumaramides based on p,p′-aromatic diamines and fumaric acid were synthesized by the phosphorylation method. The polymers were characterized by viscosity, solubility, infrared and UV-visible spectroscopy, and thermogravimetry. The fluorescence spectra of one of the polymers were studied. A model compound, fumaroyldianilide, was synthesized and characterized.
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  • 181
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2335-2343 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Glow discharge polymerization between hexamethyldisilazane (HMDSZ) and trimethylsilyldimethylamine (TMSDMA) was compared by means of infrared spectroscopy and ESCA analysis. Infrared spectra pointed out differences in chemical structure between the polymers prepared from the two monomers, although the two polymers were mainly composed of resembling units such as Si—CH3, Si—CH2, Si—H, Si—O—Si, and Si—O—C groups: (i) The polymers prepared from TMSDMA contained N → O group, but the polymers from HMDSZ did not contain this group. (ii) Influences of the W/FM parameter (W is the input energy of rf power, F the flow rate of the monomer, and M the molecular weight of the monomer) appeared on decreasing the C—N group and increasing the C=O group in the TMSDMA system, but little influence appeared in the HMDSZ system. ESCA spectra (C1s, Si2p, and N1s core levels) supported the differences between the two polymers elucidated by infrared spectroscopy, and pointed out differences in susceptibility of the Si—N bond to plasma: The N—Si sequence of TMSDMA was completely ruptured in discharge to yield polymers, and the Si—NH—Si sequence of HMDSZ remained in considerable amount.
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  • 182
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photodimerization reaction of pendant thymine bases in thymine-containing poly-lysine derivatives was studied over a wide range in aqueous solution. It was found that the quantum yield of the photodimerization of pendant thymine bases is affected mainly by the conformation of the polymers in solution. The differences in photoreaction behavior were discussed for poly-D-, poly-L-, and poly-DL-lysine derivatives.
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  • 183
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2833-2836 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Grinding chrysotile under controlled conditions results in microfibers with the dimensions of carbon black or silica agglomerates used in the reinforcement of rubber. The mechanical properties of SBR reinforced with ground asbestos are similar to those of SBR filled with a silica of equivalent surface area.
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  • 184
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2863-2872 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The small-angle, x-ray scattering method was applied to evaluate macromolecular parameters of defated proteinous silk fibers like Eri, Muga, Tussah, and raw silk. For the experimental measurement of scattering intensities the small-angle Kratky camera, coupled with an automatic-step scanning device, pulse-height discriminator, and counter attachment was used. Macromolecular parameters like specific inner surface, percentage of void, length of coherence, range of inhomogeneity, and transversal length were evaluated by using the theories of Kratky, Porod and Debye, and Bueche. The physical properties of these defated fibers were also evaluated with Scott's IP2-inclined plane tester. The correlation of the tertiary structural parameters with textile properties like average breaking strength of the proteinous fibers indicated a dependence of physical properties on certain macromolecular parameters.
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  • 185
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2873-2885 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of acid curing of epoxy resins catalyzed with tertiary amines was investigated by using model systems composed of phenylglycidyl ether and benzoic acid or acetic acid anhydrides in the presence of benzyldimethylamine. The reaction was studied by NMR spectrometry, liquid chromatography, and ozone absorption. The main findings are that (1) the tert-amine is bound chemically and irreversibly during the reaction under the formation of a quaternary ammonium salt and (2) 1-phenyloxypropanediol-2,3-dibenzoate or diacetate is the main reaction product. The suggested reaction mechanism involves initiation in which the tertiary amine reacts with the epoxy group, giving rise to a zwitterion that contains a quaternary nitrogen atom and an alkoxide anion; the latter immediately reacts with the anhydride and quaternary salt is formed. In a later stage the carboxy anion of the quaternary salt reacts first with the epoxy group, then with the anhydride. By this reaction diester is formed and the carboxy anion is regenerated.
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  • 186
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2945-2946 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 187
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2961-2972 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New polythioesters by interfacial polycondensation of bis/4-mercaptophenyl/ether with oxalyl, succinyl, adipoyl, suberoyl, or sebacoyl chlorides were obtained. To define the optimal conditions of the process, the polythioesters of dithiol and adipoyl or sebacoyl chlorides were chosen as a model system. Yield for all reaction products and reduced viscosity were found. The following factors were studied: organic phase, contribution of catalyst, concentration and molar ratio of reagents, rate of addition of acid chloride, temperature of reaction, contribution of emulsifier, and concentration of hydrochloride acceptor. The structure of all polythioesters was determined by elementary analysis, infrared spectra, and x-ray. Initial decomposition and initial intensive decomposition temperature were defined by the curves of thermogravimetric analysis. Some mechanical and electrical properties of polythioesters from dithiol and adipoyl or sebacoyl chlorides were studied. The molecular weights for these polymers were also determined by gel-chromatography.
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  • 188
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2997-3008 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of cyanomethyl methacrylate (CyMA) homopolymerization was investigated in acetonitrile with azobisisobutyronitrile as initiator. The rate of polymerization Rp was expressed by Rp = k[AIBN]0.49[CyMA]1.2 and the overall activation energy was calculated as 72.3 kJ/mol. Kinetic constants for CyMA polymerization were obtained as follows: kp/k1/2t = 0.10 L1/2s-1/2; 2fkd = 1.57 × 10-5s-. The relative reactivity ratios of CyMA(M2) copolymerization with styrene (r1 = 0.15, r2 = 0.29) and methyl methacrylate (r1 = 0.43, r2 = 0.75) in acetonitrile were obtained. Applying the Q-e scheme (in styrene copolymerization) led to Q = 1.64 and e = 0.98. The glass transition temperature Tg of poly(CyMA) was observed to be 91°C by thermomechanical analysis. Thermogravimetry of poly(CyMA) showed a 10% weight loss at 265°C in air.
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  • 189
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3027-3032 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Free-radical copolymerization of methyl acrylate (MA) with N-p-chlorophenylmaleimide (NPCMI) and N-p-bromophenylmaleimide (NPBMI) initiated by AIBN in cyclohexanone solution at 75°C was studied. The copolymer composition has been determined from the nitrogen content and NMR spectra of the copolymers. The reactivity ratios have been calculated by ML, FR, KT, and JJ methods. Q and e values of NPCMI and NPBMI have also been calculated by the Alfrey-Price Q-e scheme.
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  • 190
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3055-3061 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New silicon-containing polyimides have been prepared by the reaction of pyromellitic dianhydride (PMDA) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) with organosilicon diisocyanates having the following general structure: where R1 = R2 = —CH3 and —C6H5. Thermal properties of these polyimides were studied were by TG, DTA, and DTG.
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  • 191
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3333-3335 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 192
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3347-3352 
    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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  • 193
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3361-3371 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of action of ammonium polyphosphate (APP) and polyurea (PU) as flame retardant (FR) agents for polypropylene (PP) was examined. The APP-PU system behaves as an intumescent flame-retardant (IFR) formulation. Comparison of the oxygen index (OI) measured on molded pellets and rods, values of the polymer temperature measured just below the burning surface, and visual considerations describe the IFR action of this system. A strong synergism between APP and two of the four polyureas investigated here was ascertained with a maximum 3:1 ratio. Thermogravimetric (TG), OI, nitrous oxide index (NOI), and char-residue measurements were made. On the basis of our data, it can be concluded that polyurea acts as a catalyst for the charring reactions of the APP on PP.
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  • 194
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 183-190 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Glow-discharge polymerizations among tetramethylsilane, dimethyldimethoxysilane, and tetramethoxysilane were compared by elemental analyses and infrared spectroscopy. The elemental composition of the polymers prepared from the three monomers depended strongly on the operational conditions necessary to sustain a glow discharge, i.e., the W/FM parameter, where W is the rf power, F is the flow rate of the monomer, and M is the molecular weight of the monomer. Methoxy groups were more susceptible to glow discharge than methyl groups. Differences in chemical structure among these monomers appeared in the polymer structures formed when the glow-discharge polymerization was carried out at a low value of the W/FM parameter, while the differences disappeared at high values of the W/FM parameter, for analogous polymers. Substitution with methoxy groups was favorable for the formation of polymers of low carbon content only when the glow-discharge polymerization was performed at low values of W/FM.
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  • 195
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 227-238 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The living anions of oligomeric α-methalystyrene in THF transform to a new anion in the presence of excess monomer and UV light. Kinetic results have demonstrated that one step in this process is the second-order disappearance of monomer to form a dimeric intermediate. We have attempted to prepare this intermediate. Contrary to other reports, no hydrogen was liberated on terminating the reactions mixture with water, and an oily liquid which was identified as 1-methyl-1,3-diphenyl-cyclopentane was isolated. However, this is not the intermediate; the true intermediate is 2,5-diphenylhex-1-ene and under the conditions of the reaction the former compound is formed from this by a cyclization reaction.
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  • 196
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 293-300 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymers of viologen structure were prepared by oxidation of quinoid polymers obtained by the dimerization of alkylene dipyridinium salts with cyanide ion as catalyst. These polymers showed the behavior of polyelectrolytes and redox polymers that turn a deep blue when reduced chemically or electrically.
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  • 197
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 309-314 
    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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  • 198
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 319-328 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four aromatic dinitro compounds containing oxyethylene units 1,2-bis(4-nitrophenoxy)ethane, bis(2)-(4-nitrophenoxy)ethyl ether, 1,2-bis(2)-(4-nitrophenoxy)ethoxy)ethane, and bis(2-(2-(4-nitrophenoxy)ethoxy)ethyl) ether were prepared by an aromatic nucleophilic substitution reaction that involved 1-fluoro-4-nitrobenzene and the appropriate oxyethylene glycol. Each of the dinitro compounds could be reduced chemically or catalytically to produce the diamines 1,2-bis(4-aminophenoxy)ethane, bis(2-(4-amino-phenoxy)ethyl ether, 1,2-bis(2-(4-aminophenoxy)ethoxy)ethane, and bis(2-(2-(4-aminophenoxy)ethoxy)ethyl) ether. Polymerization of the diamines was carried out in m-cresol with toluene as an azeotroping agent. Polymides derived from 5,5′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis-1,3-isobenzofuradione exhibited good solubility in chlorinated solvents, glass transition temperatures as low as 140°C, as evidenced by viscous flow, and good thermal stability; a 5% weight loss generally occured at greater than 450°C. Isothermal aging studies conducted at 600°F(315°C) for 200 h indicated that weight loss is directly related to oxyalkylene chain length-10% for the shortest and 50% for the longest chain.
    Additional Material: 4 Ill.
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  • 199
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article describes the copolymerization of methyl vinyl ketone (MVK), methyl acrylate (MA), and methyl methacrylate (MMA) with styrene (St) as reference monomer at 3.4 MPa and 335 K with toluene as solvent. In addition, the effect of pressure on the binary copolymerizations of St-Ma-MMA is discussed. It appearsthat in case of conjugated monomers reactivity decreases as the electron-donating character of the substituents increases, whereas the reverse is found in unconjugated monomers. This is explained by the finding that in conjugated monomers resonance effects induced by polar factors play a dominant role, whereas in unconjugated monomers mainly polar factors are governing the relative reactivities. The r values at 3.4 MPa are compared with those predicted by means of the Q-e scheme and Patterns. No definite conclusions could be drawn about the applicability and validity of either scheme, although Patterns shows excellent result in case of the H function of Mayo. In vinyl ester copolymerizations and Le Noble and Asano's example of the menshutkin reaction one single factor (polarity and steric hindrance, successively) dominates ΔG#, ΔG and ΔV#. This allows a straight forward interpretation of the result with the Hammond postulate and is in full agreement with Evan's potential-energy calculations. In conjugated monomers, however, an interplay of reasonance and polar factors is found. The general validity of these findings needs further experimental and theoretical support.
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  • 200
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 385-395 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Azo compounds such as di(4-hydroxybutyl)-2,2′-azobisisobutyrate, di(3-hydroxybutyl)-2,2′-azobisisobutyrate, di(2-hydroxypropyl)-2,2′-azobisisobutyrate, and di(2-hydroxyethyl)-2,2′-azobisisobutyrate were prepared and used as initiators for the preparation of hydroxyl-terminated polybutadienes (HTPBs) of molecular weight (M̄n) ranging from 2000 to 7500 and functionality between 1.90 and 3.0. The polymers were prepared by free-radical solution polymerization in dioxane and toluene. The polymers obtained were characterized for their molecular weight, hydroxyl number, functionality, and instrinsic viscosity.
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