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1. |
Professor Dr. Dr. h.c. OTTOKRATKYzum 70. Geburtstag |
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Die Makromolekulare Chemie,
Volume 153,
Issue 1,
1972,
Page 1-4
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ISSN:0025-116X
DOI:10.1002/macp.1972.021530101
出版商:Hüthig&Wepf Verlag
年代:1972
数据来源: WILEY
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2. |
Über die elementarprozesse bei der anionischen polymerisation des styrols in tetrahydropyran (THP) |
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Die Makromolekulare Chemie,
Volume 153,
Issue 1,
1972,
Page 5-20
L. L. Böhm,
G. V. Schulz,
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摘要:
AbstractKinetische und konduktometrische Messungen am System Polystyrl‐Natrium in THP werden mit dem Ziel durchgeführt, alle in dem früher vorgeschlagenen dreiteiligen Reaktionsschema vorkommenden thermodynamischen und kinetischen Parameter zu bestimmen und mit den in anderen Lösungsmitteln gefundenen Werten zu vergleichen. Es zeigt sich, daß die Geschwindigkeitskonstanten der Monomeraddition an das Kontaktionenpaar, das solvatgetrennte Ionenpaar und das freie Anion, die sich um Größenordnungen unterscheiden, vom Lösungsmittel nur geringfügig beeinflußt werden. Der ungewöhnlich große Einfluß der Lösungsmittel auf die Polymerisationsgeschwindigkeit geschieht durch Verschiebung der Gleichgewichte zwischen den genannten Formen der Kohlenstoff
ISSN:0025-116X
DOI:10.1002/macp.1972.021530102
出版商:Hüthig&Wepf Verlag
年代:1972
数据来源: WILEY
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3. |
Thermal copolymerizations of vinyl sulfides with some weak acceptor monomers |
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Die Makromolekulare Chemie,
Volume 153,
Issue 1,
1972,
Page 21-36
Hiroshi Inoue,
Takayuki Otsu,
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摘要:
AbstractThermal copolymerizations of vinyl sulfides (VS) with some weak electron‐accepting monomers were studied on the basis of donor‐acceptor interaction. VS were thermally polymerized in the presence of diethyl fumarate, dimethyl maleate, acrylonitrile (AN) methyl methacrylate (MMA), methyl acrylate, and ethyl acrylate (EA) in the absence of radical initiators to yield copolymers. The monomer/copolymer composition curves for these copolymerizations were quite similar to those produced from polymerizations initiated by α.α′‐azobisisobutyronitrile, indicating that the propagating species are free radicals. Similar conclusions were obtained from experiments with the inhibitor benzoquinone, and from the small observed solvent effect, but no proof for the occurrence of cationic or anionic polymerization was obtained.Although the existence of a 1 : 1 donor/acceptor complex in AN/VS system was spectroscopically confirmed, such interaction was appreciably weak, in comparison to that of maleic anhydride/VS. In the systems MMA/VS and EA/VS no interaction was observed. Accordingly, the intiating radical species in AN/VS system might be considered to be formed through donor/acceptor interaction. It was also found that alternative copolymers were obtained from thermal copolymerization of AN with VS in the presence of zinc chloride. The initiation mechanism for these thermal copolymerization is
ISSN:0025-116X
DOI:10.1002/macp.1972.021530103
出版商:Hüthig&Wepf Verlag
年代:1972
数据来源: WILEY
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4. |
Radical terpolymerization of vinyl sulfide, vinyl ether, and maleic anhydride. Evaluation of the reactivities of vinyl sulfide and vinyl ether alternative copolymerization. IV |
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Die Makromolekulare Chemie,
Volume 153,
Issue 1,
1972,
Page 37-46
Hiroshi Inoue,
Takayuki Otsu,
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摘要:
AbstractThe terpolymerizations of maleic anhydride (MAn), vinyl sulfide (VS) and vinyl ether (VE) initiated by α.α′‐azobisisobutyronitrile were investigated in order to evaluate the reactivities of VS and VE toward poly(MAn) radical. Since both VS and VE undergo alternative copolymerization with MAn, these terpolymerizations were approximately treated on the basis of the free propagation and complex propagation mechanisms. From the treatment of the free propagation mechanism in which only three free monomers can participate, the reactivity of the free VS toward attack of the poly(MAn) radical was found to be 4.24 to 6.63 times higher than that of free VE, and the difference in activation energy was 1.5 kcal/mole. The higher reactivity of VS than VE might be explained by the 3 d orbital resonance between the propagating radical and the adjacent sulfur atom in VS. According to the complex propagation mechanism in which only two complexed monomers can participate, the reactivity ratios of the MAn/VS and MAn/VE complex monomers were also determined. It was found that the former complex was more reactive than the latter complex toward the poly(MAn) ra
ISSN:0025-116X
DOI:10.1002/macp.1972.021530104
出版商:Hüthig&Wepf Verlag
年代:1972
数据来源: WILEY
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5. |
Vinyl polymerization initiated by the dimethylaniline N‐oxide/tosyl chloride system |
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Die Makromolekulare Chemie,
Volume 153,
Issue 1,
1972,
Page 47-55
Tsuneyuki Sato,
Minoru Yoshioka,
Takayuki Otsu,
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摘要:
AbstractA study of the vinyl polymerization initiated by the system dimethylaniline N‐oxide (DMAO) in conjunction with tosyl chloride (TsCl) has been performed. According to the kinetic results of the polymerization of methyl methacrylate (MMA) and of the copolymerization of MMA with styrene, the polymerization proceedsviaa radical mechanism. The rate of polymerization is given by the following equation:and the overall activation energy was calculated to be 14.3 kcal · mole−1. According to the UV spectrum, the poly‐MMA obtained probably contains N‐methylanilinomethyl end groups.A graft polymer was obtained by polymerization of MMA with DMAO and partially chlorosulfonated polyethylene (Hypalon‐30). From the results an initiation mechanism is proposed and
ISSN:0025-116X
DOI:10.1002/macp.1972.021530105
出版商:Hüthig&Wepf Verlag
年代:1972
数据来源: WILEY
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6. |
Electroinitiated cationic polymerization of ethyl andi‐butyl vinyl ethers |
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Die Makromolekulare Chemie,
Volume 153,
Issue 1,
1972,
Page 57-70
Giuliano Mengoli,
Graziano Vidotto,
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摘要:
AbstractThe electroinitiated cationic polymerization of ethyl andi‐butyl vinyl ethers has been studied under various experimental conditions using NaB(C6H5)4as background electrolyte.Differring from other electrolytes with higher oxidation potentials, the NaB(C6H5)4allows appreciable current intensities and the polymerizations can occur at moderate rates.The monomer to polymer conversion presents a slightly sigmoidal shape as a function of the quantity of electricity and at a fixed quantity of electricity is independent from the current intensities.The molecular weights of the polymers are substantially controlled by chain transfer to monomers and solvents: the relative chain transfer constants are reported.The reaction temperature affects remarkably the molecular weights while the influence of dielectric constant of the reaction medium is negligible.An interpretation is given of the effect of NaB(C6H5)4electrolyte on the initiation mechanism and on the resulting conditions of polymerizatio
ISSN:0025-116X
DOI:10.1002/macp.1972.021530106
出版商:Hüthig&Wepf Verlag
年代:1972
数据来源: WILEY
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7. |
Application of dye techniques in the study of chain‐transfer properties of thiols |
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Die Makromolekulare Chemie,
Volume 153,
Issue 1,
1972,
Page 71-80
Kamal Kumar Roy,
Dinabandhu Pramanick,
Santi R. Palit,
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摘要:
AbstractDye techniques (dye partition technique in particular) have been found to be simple and sensitive methods for studying the chain transfer properties of substituted thiols containing ionic or ionogenic groups (amenable to dye test). These are: 2‐Mercapto ethanol, 2‐mercapto ethylamine hydrochloride, and thioglycolic acid. Ctrvalues obtained by this method are found to agree fairly well with those obtained from conventional DP methods. ARRHENIUS parameters and some thermodynamic functions have been evaluated from experimentally determined Ctrvalues. Existence of a negative temperature coefficient is found for the transfer process of the thiols with PMMA radicals. Transfer potency of the thiols is found to be dependent on their structure. Thus Csvalue for 2‐mercapto ethylaminehydrochloride with MMA is found to be least in the present series which can be accounted for the presence of a strong electron accepting group in the thiol which vehemently opposes the electron transfer from the thiol to the electron accpeting PMMA radical in the transition
ISSN:0025-116X
DOI:10.1002/macp.1972.021530107
出版商:Hüthig&Wepf Verlag
年代:1972
数据来源: WILEY
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8. |
Stereokontrolle. VI. Zum mechanismus der radikalischen polymerisation von methylmethacrylat |
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Die Makromolekulare Chemie,
Volume 153,
Issue 1,
1972,
Page 81-98
Paul Göldi,
Hans‐Georg Elias,
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摘要:
AbstractMethylmethacrylat wurde in Substanz und in 14 verschiedenen Lösungsmitteln bei Temperaturen zwischen −5 und +120°C radikalisch polymerisiert. Die Taxie der Polymethylmethacrylate hängt außer von der Temperatur und vom Lösungsmittel noch von der anfänglichen Monomerkonzentration ab. Die Stereokontrolle erfolgt mindestens nach einer MARKOFF‐Statistik 1. Ordnung. Zwischen je einer Differenz der Aktivierungsenthalpien (ΔH a≠− ΔH b≠) und der entsprechenden Differenz der Aktivierungsentropien (ΔS a≠− ΔS b≠) besteht unabhängig von Monomerkonzentration und Lösungsmittel ein allgemeiner Kompensationseffekt (a, b = i/i, i/s, s/i, s/s). Die Kompensationstemperatur T0ist unabhängig von der Art der Anlagerung. Die Kompensationsenthalpie ΔΔH 0≠hat den größten Wert für den Unterschied zwischen der Bildung einer isotaktischen und einer syndiotaktischen Diade an einer bereits bestehenden syndiotaktischen (s/ivs.s/s). Die Kompensationsenthalpie für die Differenz i/ivs.i/s ist dagegen praktisch gleich Null. Isotaktische Diaden bilden sich bei der Kompensationstemperatur bevorzugt an isotaktischen, syndiotaktische dagegen an syndiotaktischen. Die Tendenz zur Bildung heterotaktischer Triaden nimmt nicht in all
ISSN:0025-116X
DOI:10.1002/macp.1972.021530108
出版商:Hüthig&Wepf Verlag
年代:1972
数据来源: WILEY
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9. |
Fließverhalten und molekulare struktur von polymeren und ihren lösungen eine systematik quantitativer beziehungen |
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Die Makromolekulare Chemie,
Volume 153,
Issue 1,
1972,
Page 99-124
M. Hoffmann,
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摘要:
AbstractViskositäten bei kleinen und hohen Schubspannungen, kritische Schubspannungen der Strukturviskosität, Gummimoduli verhakter Polymerer, Konzentrationen beginnender Verhakung und Grenzviskositätszahlen hängen von Strukturparametern in quantitativer (Molekulargewicht, Uneinheitlichkeit, Konzentration, chemische Natur bzw. Kettendicke) oder in bisher erst qualitativ erkannter Weise (verschiedene Verzweigung, chemische Uneinheitlichkeit, Sequenzstruktur, Phasentrennung und Kristallisation) ab.Mehrere neue Gesetze werden mitgeteilt. Alle Beziehungen sind stärker untereinander verknüpft als bisher angenommen wurde und liefern einige phänomenologisch vergeblich gesuchte Gesetze für das Verhalten von Mischungen und L
ISSN:0025-116X
DOI:10.1002/macp.1972.021530109
出版商:Hüthig&Wepf Verlag
年代:1972
数据来源: WILEY
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10. |
Zur kenntnis der anionischen polymerisation von maleinsäureanhydrid |
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Die Makromolekulare Chemie,
Volume 153,
Issue 1,
1972,
Page 125-137
Hans Zweifel,
Jürg Löliger,
Theodor Völker,
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摘要:
AbstractIn Gegenwart von Pyridinbasen, von Triphenylphosphin oder Tributylphosphin polymerisiert Maleinsäureanhydrid spontan. Anhand eines Reaktionsmodelles wird die Bildung der beiden charakteristischen Strukturelemente in diesen Maleinsäureanhydridpolymerisaten erklärt. Die Strukturelemente der Polymeren wurden durch die analytischen Daten (IR‐, NMR‐, ESR‐Spektroskopie, Titrationen) belegt. Zum Teil wurden die Abbauprodukte isoliert und ident
ISSN:0025-116X
DOI:10.1002/macp.1972.021530110
出版商:Hüthig&Wepf Verlag
年代:1972
数据来源: WILEY
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