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  • Polymer and Materials Science  (42)
  • 1
    Electronic Resource
    Electronic Resource
    Graft copolymerization of methyl methacrylate on poly(vinyl chloride) (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 162 (1988), S. 135-148 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die chemische Modifizierung von Polyvinylchlorid (PVC) durch ein Amin verleiht dem Polymeren höhere Reaktivität gegenüber der Pfropfcopolymerisation mit einem Vinylmonomeren. Die Pfropfcopolymerisation von Methylmethacrylat auf mit n-Butylamin modifiziertes PVC wurde thermisch mit Benzoylperoxid (Bz2O2) als Initiator oder photoaktiviert mit Benzophenon (BP) als Photosensibilisator gestartet. Das aus bestimmten Experimenten erhaltene rohe Polymerprodukt wurde durch fraktionierte Fällung in die verschiedenen Bestandteile wie Polymethylmethacrylat (PMMA, Homopolymeres), PVC-g-PMMA (Pfropfcopolymeres) und unverändertes (aminiertes) PVC aufgespalten. Die getrennten Fraktionen wurden mit Hilfe der IR-Spektroskopie und der Thermogravimetrie charakterisiert. Der Mechanismus der Pfropfcopolymerisation von den beiden verschiedenen Systemen wurde erörtert. In beiden Fällen wurden Pfropfausbeuten um 30 - 70%* und Pfropfcopolymerzusammensetzungen, PMMA/PVC (w/w) zwischen 2 und 3 erhalten.
    Notes: Chemical modification of poly(vinyl chloride), PVC, by an amine renders the polymer more reactive towards graft copolymerization with a vinyl monomer. The graft copolymerization of methyl methacrylate (MMA) on PVC modified by treatment with n-butylamine (n-BA) was started thermally at 30° using benzoyl peroxide (Bz2O2) as initiator and under photoactivation at 40° using benzophenone (BP) as photo sensitizer. The gross polymer products from selected experiments were fractionally separated into the constituent polymeric entities viz., poly(methyl methacrylate), PMMA (homopolymer), PVC-g-PMMA (graft copolymer), and unreacted (aminated) PVC following a method of fractional precipitation. The separated fractions were characterized by IR spectroscopy and thermogravimetry. The mechanisms of graft copolymerization for the two different systems have been discussed. In each case, grafting efficiencies of the order of 30-70% and graft copolymers having compositions given as PMMA/PVC (w/w) equal to 2-3 were readily obtained.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051620109
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  • 2
    Electronic Resource
    Electronic Resource
    Preparation of a block copolymer by hydrolysis and subsequent oxidative coupling of the chain ends of poly(methyl methacrylate) and polystyrene, containing amidinothio end groups (1980)
    Basel : Wiley-Blackwell
    Die Makromolekulare Chemie, Rapid Communications 1 (1980), S. 149-151 
    Details
    ISSN: 0173-2803
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/marc.1980.030010304
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  • 3
    Electronic Resource
    Electronic Resource
    Photopolymerization of methyl methacrylate with the use of bromine as photoinitiator (1973)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2021-2030 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Low concentrations of bromine (0.008-0.06M) were used to initiate photopolymerization of MMA in bulk and in diluted (near bulk) systems, the diluents or solvents used being benzene, toluene, dioxane, tetrahydrofuran, carbon tetrachloride, chloroform, methylene chloride, and methanol. Polymerization in bulk follows usual free-radical kinetics. Inert solvents (benzene, toluene) as well as the other solvents used enhance the rate of polymerization MMA even when used in the range of catalytic concentrations (0.04-0.4M). An initiation mechanism involving solvent molecules appears to be predominant in diluted systems.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1973.170110821
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  • 4
    Electronic Resource
    Electronic Resource
    Photopolymerization of methyl methacrylate with the use of tetrahydrofuran-bromine charge-transfer complex as the photoinitiator (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 203-218 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of MMA was kinetically studied in the presence of visible light (using a 125-W high-pressure mercury vapor lamp with fluorescent coating, without a filter), a THF - bromine charge-transfer complex being used as the photoinitiator. The initiator exponent was 0.5 in bulk polymerization. The monomer exponent varied from about 1.2 to about 2.5, depending on the nature of the solvent used; the initiator exponent also varied in diluted systems, depending on the nature and proportion of the solvent, the variation being from a value of 0.5 in bulk system to zero or almost zero at about 25% (v/v) solvent concentration. Other kinetic parameters, viz., kp2/kt and the activation energy for polymerization, were determined and are reported. Kinetic and other evidence indicates that the photopolymerization takes place by a radical mechanism and termination is bimolecular in nature in bulk systems; in dilute systems, termination by initiator complex assumes predominance, particularly at high solvent concentrations (≥25% v/v).
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170150119
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  • 5
    Electronic Resource
    Electronic Resource
    Photopolymerization of methyl methacrylate and some other vinyl monomers with the use of a pyridine-bromine charge-transfer complex as photoinitiator (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 981-991 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of MMA was carried out under visible light (440 nm) with the use of pyridine-bromine (Py-Br2) charge-transfer (CT) complex as the photoinitiator. Initiator exponent and intensity exponent were 0.5 and 0.43, respectively, and the monomer exponent was found to be dependent on the nature of the solvent or diluent used. The Polymerization was inhibited in the presence of hydroquinone, but oxygen had very little inhibitory effect. An average value of kp2/kt for this polymerization system was 1.19 × 10-2, and the activation energy of photopolymerization was 4.95 kcal/mole. Kinetic data and other evidence indicate that the overall polymerization takes place by a radical mechanism. With Py-Br2 complex as the photoinitiator, the order of polymerizability at 40°C was found to be MMA, EMA ≫ Sty, MA.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140418
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  • 6
    Electronic Resource
    Electronic Resource
    Photopolymerization of methyl methacrylate and other vinyl monomers with the use of N-bromosuccinimide as photoinitiator (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 993-1004 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of MMA was done in the presence of visible light (440 nm) with the use of N-bromosuccinimide (NBS) as the photoinitiator. The initiator exponent and intensity exponent were 0.5, and the monomer exponent was found to be unity. The polymerization was inhibited in the presence of hydroquinone. The average kp2/kt for this photopolymerization system was found to be 0.296 × 10-2 and the activation energy of photopolymerization was 4.67 kcal/mole. Kinetic and other evidence indicate that the overall polymerization takes place by a radical mechanism. With NBS as the photoinitiator, the order of polymerizability at 40°C was MMA, EMA ≫ MA ≃ VA, and styrene could not be polymerized under similar conditions.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140419
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  • 7
    Electronic Resource
    Electronic Resource
    Benzophenone-sensitized photopolymerization of methyl methacrylate using dimethyl aniline-maleic acid combination as photoinitiator (1985)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 23 (1985), S. 1407-1419 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Benzophenone (BP)-sensitized photopolymerization of methyl methacrylate (MMA) in near UV/visible light was studied at 40°C using dimethylaniline maleic acid (DMA - MA) combination as the photoinitiator. An instantaneous 1:1 complexation between DMA and MA takes place when they are mixed together in acetonitrile. Also, instantaneous complex formation occurs between DMA and MMA and between MA and MMA when they are dissolved in MMA in low concentrations, separately. Interestingly, when equimolar proportions of DMA and MA are mixed together in MMA, there is indication for further instantaneous complexation between (DMA - MMA) complex and (MA - MMA) complex forming the actual initiating species in the photopolymerization system. Initiator exponent was 0.28 and monomer exponent varied between 0.0 to 1.8 depending on the nature of the solvent and range of dilution used. Analysis of kinetic data indicates a free radical mechanism for the polymerization with initiator-dependent termination. Chain termination via degradative initiator transfer is quite significant; but the degradative effect becomes much less prominent in the higher range of initiator concentration indicating that the reinitiation reaction following the initiator transfer process assumes more proportionate significance as the initiator concentration is increased, probably as a result of higher reinitiation efficiency. Polymers obtained gave evidence for the incorporation of aromatic (amine) end groups in them.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1985.170230514
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  • 8
    Electronic Resource
    Electronic Resource
    Photopolymerization of methyl methacrylate by use of a quinoline-bromine charge-transfer complex as the photoinitiator (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 921-930 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of MMA was carried out in presence of visible light (440 nm), quinoline-bromine charge-transfer complex being used as the photoinitiator. The initiator exponent was observed to be 0.5 up to 0.014 M initiator concentration; when chloroform was used as the solvent, the monomer exponent was found to be unity. The polymerization was inhibited in presence of hydroquinone but little inhibitory effect was observed in the presence of air. An average value of k2p/kt for this photopolymerization system was found to be (1.08 ± 0.22) × 10-2. Kinetic and other evidence indicates that the overall polymerization takes place by a radical mechanism.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130411
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  • 9
    Electronic Resource
    Electronic Resource
    Photopolymerization of methyl methacrylate and some other vinyl monomers with the use of chlorine as photoinitiator (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1531-1539 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Low concentrations (0.001-0.03M) of chlorine easily induce photopolymerization of MMA at 40°C. Kinetic data indicate that polymerization follows a radical mechanism involving complexation of monomer by the initiator and initiation takes place through radical generation during photodecomposition of the initiator-monomer complex. Termination appears to take place bimolecularly. The kp2/kt value for MMA polymerization at 40°C was found to be 0.83 × 10-2. Rates of chlorine-initiated photopolymerization were found to decrease in the order MMA, EMA ≫ VA, Sty 〉 MA.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130705
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  • 10
    Electronic Resource
    Electronic Resource
    Novel solvent effects in the photopolymerization of methyl methacrylate by use of quinoline-bromine charge-transfer complex as photoinitiator (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1743-1758 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photopolymerization of MMA was carried out at 40°C in diluted systems by use of quinolinebromine (Q-Br2) charge-transfer complex as the initiator and chloroform, carbon tetrachloride, chlorobenzene, dioxane, THF, acetone, benzene, toluene, quinoline, and pyridine as solvents. The results showed variable monomer exponents ranging from 1 to 3. For chloroform, carbon tetrachloride, and chlorobenzene, the monomer exponent observed was unity; for other solvents used, the value of the same exponent was much higher (between 2 and 3). Initiation of polymerization is considered to take place through radicals generated in the polymerization systems by the photodecomposition of (Q-Br2)-monomer complex (C) formed instantaneously in situ on addition of the Q-Br2 complex in monomer. The kinetic feature of high monomer exponent is considered to be due to higher order of stabilization of the initiating complex (C) in presence of the respective solvents. In the presence of the retarding solvents, very low or zero initiator exponents were also observed, depending on the nature and concentration of the solvents used. The deviation from the square-root dependence of rate on initiator concentration becomes higher at high solvent and initiator concentrations in general. This novel deviation is explained on the basis of initiator termination, probably via degradative chain transfer involving the solvent-modified initiating complexes and the propagating radicals.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170150722
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