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  • 1
    Electronic Resource
    Electronic Resource
    4-N,N-Dimethylamino-4'-Isopropylbenzophenone as polymerization photoinitiator. Effect of solvent and photoinitiator concentration on its photoreactivity and on the polymerization process (1990)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 28 (1990), S. 1445-1454 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several kinetics aspects of the methyl methacrylate (MMA) polymerization using 4-dimethylamino-4'-isopropylbenzophenone (PI) as photoinitiator have been studied. The order of the polymerization reaction with respect to monomer and initiator concentrations have been investigated, as well as the polymerization behavior under well-stirred and unstirred conditions; values of initiation quantum yield (φi) and kp/kt1/2 have also been determined. It has been found that the nature of the polymerization-initiating radicals depends on the type of solvent and the photoinitiator concentration ([PI]). In cyclohexane solution and at low [PI] (〈 5 x 10-5M), the cyclohexyl radical is practically the only polymerization initiating radical, while at higher [PI] both radicals, cyclohexyl and the aminoalkyl derived from PI, participate in the initiation step, increasing the participation of the later as the [PI] increases. When benzene is used as solvent both phenyl and aminoalkyl radicals participate in the initiation step at any [PI] employed. Efficiencies of the radicals derived from solvent and photoinitiator have been determined.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1990.080280612
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  • 2
    Electronic Resource
    Electronic Resource
    Synthesis of soluble polymeric photosensitizers with the 4-nitro-1-naphthyl-carbamoyl as pendant group (1990)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 28 (1990), S. 3499-3511 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several models of monomers, homopolymers, and copolymers containing a photosensitizer group, 4-nitro-1-naphthyl-carbamoyl (NNC), have been synthesized. Synthetic methods are described, in addition to two routes for copolymers preparation. First, the radical copolymerization between monomers with the photosensitizer group built-in and comercial monomers such as styrene and methyl acrylate and, second, polymer modification by nucleophilic reaction between carbonyl group polymer supported and nitro-naphthyl amine. All products were characterized and one of the resulting soluble polymeric photosensitizer and its model compound, were tested as triplet energy donors against trans- stilbene and their Stern-Volmer constants were determined. Results show that the sensitizer efficiency is closer to that of the well known benzophenone sensitizer and higher than that of the acetophenone, while the sensitizer efficiency disminished when the chromophore is bonded to the polymer.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1990.080281225
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  • 3
    Electronic Resource
    Electronic Resource
    Photochemical behavior of p-dimethylaminobenzoylated polystyrene as polymerization photoinitiator: Synthesis of graft copolymers (1993)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 153-157 
    Details
    ISSN: 0887-624X
    Keywords: polymeric photoinitiators ; photopolymerization ; graft copolymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemical behavior of p-dimethylaminobenzoylated polystyrene (PS-MI) in benzene solution has been investigated, both in the presence and absence of methyl methacrylate (MMA). This behavior has been compared with that of the model compound, 4-isopropyl-4′-N,N-dimethylaminobenzophenone (CU-MI). PS-MI photoreduction takes place only through excimer formation due to the high local chromophore concentration, and therefore, PS-MI disappearance quantum yield is close to the previously calculated limiting value (0.02) and independent of chromophore concentration. Several parameters that characterize the polymerization process have been determined; it has been found that the obtained PMMA is photografted onto PS-MI backbone. This is in agreement with the proposed mechanism for radical generation. No homo-PMMA formation has been detected. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1993.080310118
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  • 4
    Electronic Resource
    Electronic Resource
    Reactivity of radicals from 1-(N,N-dimethylamino)ethylene-2-derivatives in the acrylic photopolymerization (1997)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2889-2899 
    Details
    ISSN: 0887-624X
    Keywords: radical efficiency calculation ; photoinitiated polymerization ; Taft correlation ; structure-reactivity relationships ; quantum semiempirical calculations ; Ab initio calculations ; molecular orbitals ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative reactivities of radicals derived from several 1-(N,N-dimethylamino)ethylene-2-derivatives towards the polymerization of butyl acrylate have been calculated. It has been observed that the reactivity of the radicals increases as the electron withdrawing character of the groups attached in the β position to the N atom increases. The experimental efficiency factor (f) has been found to be proportional to the σF value defined in the Taft equation. The dependence of the reactivities with the nature of the radicals has also been explained through their frontier orbital characteristics. The presence of heteroatoms next to the radical center could modify, in some cases, the accuracy of these calculations, although the inclusion of more sophisticated quantum-mechanical methods does solve this drawback. Moreover, the enthalpy calculation of the possible radicals formed from a certain molecule gives a good approach to realize about the existence of anomalous behaviors. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2889-2899, 1997
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Novel dialkylaminoalkyl- and dialkylaminoalcoxi-benzophenones as photoinitiators of polymerization. I. Photochemical characteristics and radical efficiencies (1991)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 29 (1991), S. 1955-1961 
    Details
    ISSN: 0887-624X
    Keywords: photoinitiation ; alkylaminobenzophenones ; radical efficiencies ; photopolymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The behavior of the nonconjugated aminated benzophenones - 4-[2′-N,N-(diethylamino)ethoxy]benzophenone (E4), 2-[2′-N,N-(diethylamino)ethoxy]-4-methoxybenzophenone (E2), and 4-N,N-dimethylaminomethylbenzophenone (DM) - as photoinitiators of MMA polymerization has been studied and the results compared with those obtained with the conjugated aminobenzophenone 4-N,N-dimethylamino-4′-isopropyl-benzophenone (CU - MI). Photoreduction behavior of these compounds in various solvents in the presence and absence of MMA has been also examined. The order of the polymerization reaction with respect to monomer and initiator concentrations has been investigated; values of initiation quantum yield (Φi), Kp/K1/2t and efficiencies of the different radicals have also been determined. Similar polymerization rates (Rp) of methyl methacrylate (MMA) were found when E4 and CU-MI were used as photoinitiators under the same range of absorbed irradiation intensity. This fact results from a compensation between the higher rate of E4 radical production (n-π* transition type) and the greater reactivity of the radicals generated from CU-MI.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1991.080291316
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  • 6
    Electronic Resource
    Electronic Resource
    Photopolymerization of hydroxyethylmethacrylate in the formation of organic-inorganic hybrid sol-gel matrices (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 3289-3296 
    Details
    ISSN: 0887-624X
    Keywords: photoinitiation ; photopolymerization ; sol-gel matrices ; hybrid materials ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydroxyethylmethacrylate (HEMA) monomer in different contents was used in the preparation of transparent organic-inorganic hybrid sol-gel matrices. The matrices were studied by analytical techniques before and after irradiation. An increase in the homogeneity of the composite material after the irradiation of HEMA, and a chemical linkage of the monomer with the surface has been observed. Photopolymerization processes were studied by differential scanning calorimetry (DSC). Details of the irradiation times, polymerization rates, and DSC related parameters of HEMA in the sol-gel matrices are reported. © 1996 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Kinetic investigations on the photopolymerization of di- and tetrafunctional methacrylic monomers in polymeric matrices. ESR and calorimetric studies. II. Postpolymerization reactions (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2785-2791 
    Details
    ISSN: 0887-624X
    Keywords: postpolymerization reactions ; ESR ; polymeric matrices termination reactions ; H-transfer reactions ; kinetic constants ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction kinetics in the dark of photopolymerized mono- and dimethacrylates in a polymeric binder has been studied. Electron spin resonance spectroscopy (ESR) provided useful information regarding the nature of the radicals involved in postpolymerization reactions. Computer simulations were performed to study the decay of the propagating radicals by considering normal bimolecular termination and transfer reactions of the radicals to the binder. Differences were found in the termination reactions for mono- and difunctional monomers when they were photopolymerized in a solid medium. Absolute kinetic constants for H-transfer reaction with the binder, relative kinetic rate constants for radical-radical coupling, and average lifetimes for the radicals have been calculated. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2785-2791, 1998
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Radical copolymerization of 2-acryloyl thioxanthone with methyl methacrylate (1990)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 28 (1990), S. 967-972 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel monomer, 2-acryloyl thioxanthone (TXA), was prepared by reaction of 2-hydroxy thioxanthone with acryloyl chloride. Copolymerization of TXA with methyl methacrylate (MMA) in DMF at 80°C was studied in order to evaluate relative reactivities of these monomers. Values of 1.36 and 0.5 were found for the respective reactivity ratios of MMA and TXA, respectively. The resonance stabilization and polar properties were determined and discussed in terms of spectroscopic data.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1990.080280502
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  • 9
    Electronic Resource
    Electronic Resource
    Mechanism of photostabilization of polystyrene film by dihydroxyphenyl-pirazoles (1990)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 28 (1990), S. 3661-3668 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new family of ultraviolet absorbers, the dihydroxyphenyl-pyrazoles, has shown to be able to act as photostabilizers of polymers. In the present work the efficiency of the derivative 2,5 bis(pyrazol-1′-yl)-1,4-dihydroxybenzene (BPHB) in preventing the photooxidative degradation of polystyrene films have been measured. The effect of light screening on polymer photostabilization was examined by using external filter solutions of BPHB and it was found that it does not function simply as a light screener. Phosphorescence quenching experiments show that BPHB behaves also as an efficient triplet-state quencher of the polymer in-chain carbonyl impurity groups, which play an important part in the overall mechanism of light stabilization.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1990.080281312
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    Paper (German National Licenses)
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetic investigations on the photopolymerization of di- and tetrafunctional (meth)acrylic monomers in polymeric matrices. ESR and calorimetric studies. I. Reactions under irradiation (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2775-2783 
    Details
    ISSN: 0887-624X
    Keywords: photopolymerization kinetics ; ESR ; polymeric binders ; radical environment ; photocalorimetry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photopolymerization of several di- and tetrafunctional (meth)acrylic monomers in the presence of a styrene-butadiene-styrene polymeric matrix (SBS) has been studied. Electron spin resonance spectroscopy (ESR) and differential scanning photocalorimetry (photo-DSC) were used as monitoring techniques to identify the photogenerated radicals and analyze photopolymerization profiles, radical environments, and radical secondary reactions. The study of the photopolymerization and/or photocrosslinking reactions of these monomers in the solid media was carried out by taking into consideration different factors, such as the influence of both monomer and photoinitiator structures on the hydrogen abstraction in the binder with formation of benzylic and allylic radicals, the polymerization of the monomers itself and the hydrogen abstraction reaction in the polymerized acrylic chains. Finally, irradiation of the system SBS/photoinitiator in the absence of monomer was also accomplished. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2775-2783, 1998
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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