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  • 1
    Electronic Resource
    Electronic Resource
    Chain Transfer by an Addition-Substitution-Fragmentation Mechanism. 2. Preparation of .alpha.,.omega.-Difunctional Telomers through a radical transfer reaction on a Methacrylic-Type Cyclic Peroxyketal (1994)
    s.l. : American Chemical Society
    Macromolecules 27 (1994), S. 5972-5978 
    Details
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/ma00099a007
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  • 2
    Electronic Resource
    Electronic Resource
    Synthesis and properties of poly(2,4,6-trimethylstyrene) (1979)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 180 (1979), S. 2061-2071 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2,4,6-Trimethylstyrene (3a) was found to be polymerizable anionically yielding well defined samples of poly(2,4,6-trimethylstyrene) (4) with low polydispersity, provided the reaction is carried out at low temperature in a polar solvent. It could be demonstrated that the bulkiness of the trimethylphenyl substituents in this polymer is responsible for the somewhat enhanced rigidity of the chain, and for the increase of the glass transition temperature with respect to polystyrene and to some other methyl substituted polystyrenes.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1979.021800901
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  • 3
    Electronic Resource
    Electronic Resource
    Etude de la polycondensation linéaire de polymères précurseurs α,ω-bifonctionnels avec des agents de couplage bifonctionnels de faible masse molaire (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2647-2661 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chain extension reactions involving α,β-bifunctional precursor polymers and bifunctional coupling agents of low molecular weight were investigated both theoretically and experimentally. The number and weight molecular weight distributions were calculated, and computer simulations were performed, neglecting the weight of the coupling agent with respect to that of the precursor polymer. Examples of such chain extension reactions include the polycondensation of “living” α,β-dicarbanionic polystyrene with 1,4-bis(bromomethyl)benzene, and the reaction of poly(oxyethylene)glycol with a low-molecular-weight diisocyanate. The characterization of the resulting polymers yields results that are in satisfactory agreement with the theoretical expectation.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021851215
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  • 4
    Electronic Resource
    Electronic Resource
    Etude de la simulation des réactions de polycondensation par la méthode de Monte-Carlo (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 2321-2335 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Simulation of polycondensation reactions using a Monte-Carlo type method is discussed in detail. The process applies to reactions carried out in homogeneous isotropic phase and it is valid regardless of the number of constituents involved, and whatever the reactivity of the individual functions may be. However, it does not include cyclization, and cannot take into account the variation of the reactivity of a given function with conversion. The conditions that should be satisfied are discussed thoroughly; in particular, duplication procedures are introduced at various stages of the reaction to prevent the system from becoming too small at high conversion. The method was tested on two rather simple cases: the self condensation of AB-type monomer molecules, and chain extension involving AA-type macromolecules and BB-type micromolecular coupling agents. The agreement between the simulation and the data of the classical polycondensation theory is very satisfactory.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.021861113
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  • 5
    Electronic Resource
    Electronic Resource
    Synthesis and characterization of hetero-arm star copolymers (1990)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 191 (1990), S. 2319-2328 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hetero-arm star copolymers are constituted of a central core carrying branches of two kinds. The two-stage synthesis of such polymer species involves an arm-first step and a core-first step: A linear anionic living polystyrene precursor was used to initiate the polymerization of a small amount of divinylbenzene, yielding star-shaped polystyrene bearing living sites inside the cores; in a second stage these sites were used to initiate the polymerization of another monomer  -  butyl methacrylate  - , more electrophilic than styrene. This second step results in the formation of a new set of branches originating from the same polydivinylbenzene cores. The star polystyrenes, and the hetero-arm star copolymers were characterized adequately, and their molecular weights were found to be in satisfactory agreement with expectation. The presence of some remaining linear precursor in the star polymer samples is discussed thoroughly on the basis of a detailed computerized analysis of the size exclusion chromatograms of both the star polystyrene samples and the hetero-arm star copolymers.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1990.021911010
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  • 6
    Electronic Resource
    Electronic Resource
    Synthèse et propriétés du poly(p-triméthylsilystyrène) (1982)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 183 (1982), S. 1181-1190 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: p-Trimethylsilylstyrene was found to be polymerisable anionically. When the reaction is carried out at low temperature in THF as solvent the polymer - poly(p-trimethylsilylstyrene) - is obtained in a quantitative yield and exhibits a low polydispersity. The glass transition temperature, viscosity-molecular weight relationships, and 1H and 13C NMR spectra were investigated in order to compare the influence of the trimethylsilyl group located at the benzene nucleus with respect to polystyrene and some other p-subtituted polystyrenes. The presence of the trimethylsilyl group in para position of the aromatic nucleus results in an increase of the rigidity of the polymer chain and in an increase of the glass transition temperature.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1982.021830512
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  • 7
    Electronic Resource
    Electronic Resource
    Macromonomers: A new class of polymeric intermediates in macromolecular synthesis - IIPart 1 : see reference 4 - homo- and copolymerizationDedicated to Professor Georges Smets with best regards (1985)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 13 (1985), S. 47-66 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper deals with the ability of macromonomers to undergo polymerization and copolymerization with vinylic or acrylic comonomers.Polymacromonomers have been made by free radical or by anionic polymerization techniques. The species formed are branched, and characterized by high segment densities, which imply that their molecular dimensions are smaller than those of linear homologues of the same molecular weight.The free radical copolymerization of various types of macromonomers with low molecular weight comonomers was investigated kinetically. The graft copolymers obtained are homogeneous in composition, as it could be anticipated from the mole ratio of macromonomer to monomer used. Special emphasis was given to amphiphilic species, made of hydrophilic grafts attached to a hydrophobic backbone. These copolymers exhibit a strong tendency to form stable emulsions.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1985.020131985105
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  • 8
    Electronic Resource
    Electronic Resource
    Chain transfer by addition-substitution-fragmentation mechanism. I. End-functional polymers by a single-step free radical transfer reaction: Use of a new allylic linear peroxyketal (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2687-2697 
    Details
    ISSN: 0887-624X
    Keywords: free radical polymerization ; transfer reaction ; addition-substitution-fragmentation mechanism ; end-group functionalisation ; allylic peroxyketal ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new chain transfer agent, ethyl 2-[1-(1-n-butoxyethylperoxy) ethyl] propenoate (EBEPEP) was used in the free radical polymerization of methyl methacrylate (MMA), styrene (St), and butyl acrylate (BA) to produce end-functional polymers by a radical addition-substitution-fragmentation mechanism. The chain transfer constants (Ctr) for EBEPEP in the three monomers polymerization at 60°C were determined from measurements of the degrees of polymerization. The Ctr were determined to be 0.086, 0.91, and 0.63 in MMA, St, and BA, respectively. EBEPEP behaves nearly as an “azeotropic” transfer agent for styrene at 60°C. The activation energy, Eatr, for the chain transfer reaction of EBEPEP with PMMA radicals was determined to be 29.5 kJ/mol. Thermal stability of peroxyketal EBEPEP in the polymerization medium was estimated from the DSC measurements of the activation energy, Eath = 133.5 kJ/mol, and the rate constants, kth, of the thermolysis to various temperature. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321409
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  • 9
    Electronic Resource
    Electronic Resource
    Chain transfer by addition-fragmentation mechanism. VII.For Part VI, see Reference 1. Radical polymerization of vinyl monomers in the presence of ethyl 2-[1-(trimethylsilylperoxy)ethyl]propenoateSystematic name: 1, ethyl 2-methylene-3-trimethylsilyl-dioxybutanoate. and related compounds (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 893-902 
    Details
    ISSN: 0887-624X
    Keywords: chain transfer ; addition-fragmentation ; peroxysilane ; radical polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethyl 2-[1-(trimethylsilylperoxy)ethyl]propenoate 1, ethyl 2-[1-(dimethylvinylsilylperoxy)-ethyl]propenoate 2, ethyl 2-[1-(1-(2-ethoxycarbonyl-1-methyl-2-propenylperoxysilyl)-1-methylethylperoxy)ethyl]propenoate 3, and 2-phenyl-2-trimethylsilylperoxypropane 4 were synthesized and added to the free radical polymerization of vinylic monomers. 1 and 2 were found to show no homopolymerizability but act as effective chain transfer reagents in radical polymerizations of methyl methacrylate (MMA), styrene (St), and n-butyl acrylate (BA). The estimated chain transfer constants (Ctr) are as follows: Ctr (1) = 0.15 for MMA, 0.90 for St, and 2.03 for BA at 60°C; Ctr (2) = 0.12 for MMA, 1.16 for St, and 1.9 for BA at 60°C. 1H-NMR spectra of poly(St) formed in the presence of 1 is consistent with the view that the polymers bear an oxirane at one terminal and an trimethylsilyloxy fragment at the other end. Moreover, peroxysilane 4 showed very low transfer properties by direct homolytic substitution (SH2). These findings indicate that the ethyl 2-[1-(substituted dimethylsilylperoxy)ethyl]-propenoates 1-3 undergo chain transfer reaction via a intramolecular homolytic substitution (SHi) following an addition process. Preparation of poly(styrene) up to high conversion in the presence of 3 yielded to the formation of the corresponding polymeric structures bearing hydrolysable C(SINGLE BOND)O(SINGLE BOND)Si(SINGLE BOND)O(SINGLE BOND)C bonds. © 1996 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Synthesis, characterization and hydrolysis of poly[styrene-co-(6-methylene-1,4-oxathiepane-7-one)] and poly[styrene-co-(6-methylene-5-methyl-1,4-oxathiepane-7-one)] (1998)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 2577-2582 
    Details
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Vinylic-type polymers bearing ester groups inside the polymer backbone have been synthesized by free radical copolymerization of styrene (St) and 6-methylene-1,4-oxathiepane-7-one (MOTPO) or 6-methylene-5-methyl-1,4-oxathiepane-7-one (MMOTPO). The addition-fragmentation ring-opening polymerization of both MOTPO and MMOTPO leads to the formation of ester linkages located inside the vinylic polymer backbone. A strong decrease of the molar mass of the copolymer has been observed when the copolymers were dissolved in a mixture of THF and water in the presence of sodium hydroxide. This decrease can be attributed to the hydrolysis of the ester linkages, as followed by size exclusion chromatography (SEC). The molar mass of the degraded polymer samples was correlated with the number of ester linkages in the backbone, showing that only a fraction of these ester groups have been hydrolyzed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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