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  • 1
    ISSN: 1520-510X
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2315-2327 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methacryloyl-L-valine methyl ester (MAVM) and maleic anhydride (MAn) were photopolymerized without initiator in dioxane at 35°C. Copolymer having a 1:1 molar ratio of the monomers was obtained regardless of both molar ratio of monomers in the feed and polymerization time. The circular dichroism (CD) spectrum of the copolymer before and after hydrolysis showed the induction of asymmetric centers into the polymer main chain. Spectroscopic and kinetic studies suggested the alternating and stereoregular copolymerization of MAVM and MAn, in which a charge transfer complex with a 1:1 molar ratio of monomers participated.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 3171-3179 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photocopolymerization of methacryloyl-L-valine methyl ester (L-MAVM), methacryloyl-D-valine methyl ester (D-MAVM) and maleic anhydride (MAn) was carried out in dioxane at 25°C without initiator at an initial total concentration of the three monomers of 1 mole/1.; the molar ratio of MAn in the feed to the sum of L- and D-MAVM was 1 : 1 in all cases. The copolymer with a 1 : 1 molar ratio of MAVM and MAn was always obtained regardless of the feed molar ratio of L- and D-MAVM. The circular dichroism (CD) spectra of the copolymer before and after hydrolysis showed a linear relationship between the monomer unit ellipticity at 222 nm and the molar feed ratio of L- and D-MAVM and suggested the induction of an asymmetric center into the polymer main chain. The results also indicated that the configuration of the induced asymmetric carbon atoms would be arranged according to that of fed MAVM monomer.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 785-792 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Maleic anhydride (MAn) was irradiated with ultraviolet light in dioxane at 35°C without initiator, and predominantly a MAn oligomer was obtained with a small quantity of cyclic dimer of MAn. Mass spectrometric, NMR, and elementary analysis investigation of the oligomer showed that it is composed of about four MAn units and one dioxane molecule per molecule.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 57-65 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stereochemical composition of an alternating methacryloyl-L-valine methyl estermaleic anhydride (L-MAVM/MAn) copolymer which was prepared by the photocopolymerization of L-MAVM and MAn in dioxane at 25°C without initiator was investigated by proton magnetic resonance spectroscopy. The resonance of the ester methyl protons of the L-MAVM unit appeared as three split peaks at 3.65, 3.76, and 3.82 ppm, which could be assigned to those of the coisotactic (di-threo-tri-isotactic), coheterotactic and cosyndiotactic triads, respectively. The triad cotacticity determined according to these assignments indicated that the copolymer was composed predominantly of di-threo-tri-isotactic triad. Similarly PMR spectroscopic investigation of the acryloyl-L-valine methyl ester-maleic anhydride (L-AVM/MAn) copolymer with a 1:1 molar ratio of the monomers showed that the main tactic fraction of the copolymer was also di-threo-tri-isotactic one. Nevertheless, the circular dichroic investigation of the L-AVM/MAn copolymer before and after hydrolysis denied asymmetric induction into the polymer main chain. These results suggest that the propagation step in the photocopolymerization of L-MAVM or L-AVM with MAn proceeds by the trans-trans opening of the complexmer composed of a 1:1 molar ratio of L-MAVM or L-AVM and MAn.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1787-1797 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photosensitized copolymerization of optically active N-l-menthylmaleimide (NMMI) with styrene (Sty) and methyl methacrylate (MMA) was carried out in tetrahydrofuran (THF) at 30°C with benzoyl peroxide (BPO). The monomer reactivity ratios for the copolymerization of NMMI (M2) with Sty (M1) and MMA (M1) were r1 = 0.08 ± 0.10, r2 = 0.20 ± 0.05 and r1 = 2.85 ± 0.06, r2 = 0.07 ± 0.06, respectively. Copoly-MMA-NMMI and poly-NMMI showed positive circular dichroism(CD) curves of equal intensity and shape over the wavelength region from 230 to 270 nm; copoly-Sty-NMMI also showed a positive CD curve which was similar in shape but was different in intensity from that of poly-NMMI. The correlation between monomer unit ellipticity of the copolymers and their composition would suggest the alternating and stereoregular copolymerization of NMMI with Sty.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 12 (1974), S. 503-507 
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 129 (1969), S. 47-55 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine kinetische Untersuchung der durch Trichloracetylchlorid (TAC) und Wasser initiierten Polymerisation von Methylmethacrylat (MMA) wurde dilatometrisch durchgeführt. Die Reaktion verläuft über einen Radikalmechanismus; die Anfangspolymerisationsgeschwindigkeit wird durch folgende Gleichung wiedergegeben: \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R}_{\rm p} {\rm = k[MMA][TAC - H}_{ 2} { O]}^{{ 0}{ .45}}. $\end{document} Die Bruttoaktivierungsenergie der Initiierung wurde auf 4,8 kcal/Mol geschätzt. Aus den kinetischen Ergebnissen und den Daten der Flüssig-Gas-Chromatographie wird ein wahrscheinlich erscheinender Initiierungsmechanismus vorgeschlagen.
    Notes: A kinetic study on the polymerization of methyl methacrylate (MMA) initiated by trichloroacetyl chloride (TAC) and water was made dilatometrically. The reaction proceeds by a radical mechanism, and the initial rate of polymerization is described by the equation: \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R}_{\rm p} {\rm = k[MMA][TAC - H}_{ 2} { O]}^{{ 0}{ .45}}. $\end{document} The overall activation energy of the initiation was estimated as 4.8 kcal/mole. A probable initiation mechanism was proposed from the kinetic results and the liquid gas chromatographic data.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 129 (1969), S. 56-62 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die durch Trichloracetylchlorid (TAC) und Wasser initiierte Polymerisation von Styrol wurde untersucht. Die Reaktion verlief über einen ionischen Mechanismus, und es bildeten sich Polymere von verhältnismäßig niederem Molekulargewicht. Auf Grund der analytischen Daten des Polymeren wird angenommen, daß die ionische Zersetzung eines als Zwischenprodukt vorliegenden Komplexes aus TAC und Wasser Trichloressigsäure ergibt, die die kationische Polymerisation des Styrols herbeiführt.
    Notes: The polymerization of styrene initiated by trichloroacetyl chloride (TAC) and water was investigated. The reaction proceeded by an ionic mechanism and polymers of relatively low molecular weight were formed. From the analytical results of the polymer, it was suggested that the ionic decomposition of an intermediate complex formed by TAC and water yielded chloroformic acid which induced cationic polymerization of styrene.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 161 (1972), S. 173-184 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kinetik der Photopolymerisation von Methylmethacrylate (MMA) in Gegenwart eines Trirhodanidtripyridin-Eisen(III)-Komplexes (Fe[SCN]3Py3) wurde untersucht. Die Bruttogeschwindigkeit (Rp) der Photopolymerisation läßt sich durch die Beziehung \documentclass{article}\pagestyle{empty}\begin{document}$${\rm R}_{\rm p} = {\rm k}\left[ {{\rm Fe}({\rm SCN})_3 {\rm Py}_3 } \right]^{0.45} \left[ {{\rm MMA}} \right]^{1.50}$$\end{document} darstellen. Der für kp/kt1/2 erhaltene Wert steht in befriedigender Übereinstimmung mit den schon bekannten Werten für die radikalische Polymerisation von MMA. für die Bruttoaktivierungsenergie der Polymerisation ergab sich ein Wert von 3,0 kcal/Mol, während für die Größe Ep - 1/2 Et aus einer Auftragung von log kp/kt1/2 gegen l/T ein Wert von 3,1 kcal/Mol erhalten wurde.Diese kinetischen Befunde und die Zusammensetzung von MMA/Styrol-Copolymeren zeigen, daß die Photopolymerisation mit dem Eisen(III)-Komplex über einen radikalischen Mechanismus verläuft und daß das Monomere am Startschritt beteiligt ist.
    Notes: The photopolymerization of methyl methacrylate (MMA) in the presence of trithiocyanatotripyridine iron(III) complex (Fe(SCN)3Py3) was kinetically studied. The overall rate of photopolymerization (Rp) in ethanol at 35°C was shown as following: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm R}_{\rm p} = {\rm k}\left[ {{\rm Fe}({\rm SCN})_3 {\rm Py}_3 } \right]^{0.45} \left[ {{\rm MMA}} \right]^{1.50}$$\end{document}The obtained value of kp/kt1/2 was satisfactorily consistent with those reported for the radical polymerization of MMA hitherto. The overall activation energy of the polymerization was calculated to be 3.0 kcal/mole, and the value of Ep - 1/2 Et obtained from the log kp/kt1/2 versus l/T curve was 3.1 kcal/mole.These kinetic data and the composition curve of the copolymerization of MMA and styrene showed that the photopolymerization with the iron(III) complex proceeded via a free radical mechanism and that the monomer participated in the initiation step.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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