ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLiving radical polymerization of styrene with tetramethylene disulfideKiyoshi Endo, Kiyoshi Murata, and Takayuki OtsuCite this: Macromolecules 1992, 25, 20, 5554–5556Publication Date (Print):September 1, 1992Publication History Published online1 May 2002Published inissue 1 September 1992https://doi.org/10.1021/ma00046a072Request reuse permissionsArticle Views466Altmetric-Citations56LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (271 KB) Get e-Alertsclose Get e-Alerts
This review describes thermal polymerization of cyclic disulfides without any initiators. Cyclic disulfides such as 1, 2-dithiane (DT) and 1, 4-dihydro-2, 3-benzodithine (XDS) can polymerize easily at reaction temperature of the melting points of the respective monomers to give a high molecular weight polymer determined by GPC. From the analyses of NMR and ESI-MS spectroscopies, the polymers obtained from the polymerization of cyclic disulfides were found to be a cyclic structure. Moreover, thermal and mechanical properties of the polymers, and decomposition behaviors of the polymers demonstrate that the polymers obtained from thermal polymerization of cyclic disulfides include a polycatenane structure. From polymerization of cyclic disulfides in the presence of cyclic poly (ethylene oxide), a polycatenane consisting of two different cyclic polymer was obtained. The polymers revealed characteristics as a shape-memory material.
Abstract Copolymerization of styrene (St) and isoprene (IP) with nickel(II) acetylacetonate [Ni(acac) 2 ] and methylalumoxane (MAO) catalyst was investigated. It was found that the Ni(acac) 2 ‐MAO catalyst is effective for the copolymerization of St and IP. From the copolymerization of St (M 1 ) and IP (M 2 ) and IP (M 2 ) with the Ni(acac) 2 ‐methylalumoxane catalyst, the monomer‐reactivity ratios were determined to be r 1 = 1,18 and r 2 = 0,88, i.e., ideal copolymerization was found to proceed to give perfectly random copolymers without formation of any homopolymer. The microstructure of IP units in the copolymers exhibits high cis‐1,4 contents.
Synthesis of polymers containing disulfide bonds in the main chain by electrochemical polymerization of 1,10-decanedithiol (DEDT) in acetonitrile (CH3CN) at constant current was investigated. The electrochemical polymerization of DEDT proceeded easily to give a polymer containing disulfide bonds in the main chain formed by intermolecular coupling reaction in good yields. The polymer yield was proportion to both Faradaic charge and DEDT concentration in the feed, but the M̄n of the polymer remained almost constant during the reaction. On the addition of benzylthiol (BzSH) to the electrochemical polymerization of DEDT, the polymer yield decreased, whereas the polymer yield increased when dibenzyldisulfide (DBDS) was added to the polymerization of DEDT. The benzylthiyl anion derived from DBDS seems to promote the formation of an S—S bond. The content of benzylthiyl derived from DBDS at the chain end was proportion to the amount of DBDS added.
Abstract The kinetics of monomer‐isomerization polymerizations of cis ‐2‐butene with TiCl 3 /Al(C 2 H 5 ) 3 catalysts in the presence and absence of NiCl, was studied. Both the rate of isomerization and polymerization increased as a function of the concentrations of the monomer and catalyst. The apparent activation energies for the polymerization with TiCl 3 /Al(C 2 H 5 ) 3 and with TiCl 3 /NiCl 2 /Al(C 2 H 5 ) 3 were estimated to be 25,6 and 17,2 kJ/mol, respectively. This difference in the apparent activation energy for monomer‐isomerization polymerization may be accounted for by the rates of isomerization to 1‐butene. The reaction constants for the isomerization and polymerization were evaluated by simulation. The rate of polymerization with the TiCI 3 /Al(C 2 H 5 ) 3 catalyst was found to be about 40 times higher than that of isomerization, and in the presence of NiCl 2 , both rates become similar. From product analysis produced with TiCl 3 and alkylaluminium compounds, it is concluded that the active sites for isomerization involve Ti 2+ complexes and those for the polymerization involve Ti 3+ complexes.
