Synthesis and characterization of an exact comb polyisoprene with three branches having the middle branch twice the molecular weight of the other two identical external branches

Handle URI:
http://hdl.handle.net/10754/562543
Title:
Synthesis and characterization of an exact comb polyisoprene with three branches having the middle branch twice the molecular weight of the other two identical external branches
Authors:
Ratkanthwar, Kedar ( 0000-0002-6324-696X ) ; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 ) ; Lee, Sanghoon; Chang, Taihyun; Pudukulathan, Zubaidha; Vlassopoulos, Dimitris
Abstract:
An exact comb polyisoprene (PI) with three branches, with the middle branch having twice the molecular weight of the two other identical external branches, was synthesized by using anionic polymerization high vacuum techniques and appropriate chlorosilane chemistry. The synthetic approach involves (a) the selective replacement of the two chlorines of 4-(dichloromethylsilyl) diphenylethylene (DCMSDPE, key molecule) with identical PI chains by titration with PILi, (b) the addition of sec-BuLi to the double bond of DPE followed by the polymerization of isoprene from the newly created anionic site to form a 3-arm living star PI, (c) the selective replacement of the two chlorines of trichloromethylsilane with 3-arm star PI to form an H-shape intermediate, and (d) the replacement of the remaining chlorine of trichloromethylsilane by linear PI chains with double the molecular weight. All intermediate and final products were characterized via size exclusion chromatography, temperature gradient interaction chromatography and 1H-NMR spectroscopy. As expected, due to the inability to control the exact stoichiometry of the linking reactants, the main product (exact comb PI) is contaminated by a few by-products, despite the fact that anionic polymerization is the most efficient way to produce well-defined polymers. © 2013 The Royal Society of Chemistry.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program; Polymer Synthesis Laboratory
Publisher:
Royal Society of Chemistry
Journal:
Polymer Chemistry
Issue Date:
2013
DOI:
10.1039/c3py00848g
Type:
Article
ISSN:
17599954
Sponsors:
KR is thankful to the Industrial Chemistry Laboratory of the University of Athens for providing guidance and laboratory facilities, as well as to the Marie-Curie DYNACOP (PITN-GA-2008-214627) project for financial support. TC acknowledges the supports from NRF (2008-0061892 and 2012R1A2A2A01015148).
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorRatkanthwar, Kedaren
dc.contributor.authorHadjichristidis, Nikolaosen
dc.contributor.authorLee, Sanghoonen
dc.contributor.authorChang, Taihyunen
dc.contributor.authorPudukulathan, Zubaidhaen
dc.contributor.authorVlassopoulos, Dimitrisen
dc.date.accessioned2015-08-03T10:42:02Zen
dc.date.available2015-08-03T10:42:02Zen
dc.date.issued2013en
dc.identifier.issn17599954en
dc.identifier.doi10.1039/c3py00848gen
dc.identifier.urihttp://hdl.handle.net/10754/562543en
dc.description.abstractAn exact comb polyisoprene (PI) with three branches, with the middle branch having twice the molecular weight of the two other identical external branches, was synthesized by using anionic polymerization high vacuum techniques and appropriate chlorosilane chemistry. The synthetic approach involves (a) the selective replacement of the two chlorines of 4-(dichloromethylsilyl) diphenylethylene (DCMSDPE, key molecule) with identical PI chains by titration with PILi, (b) the addition of sec-BuLi to the double bond of DPE followed by the polymerization of isoprene from the newly created anionic site to form a 3-arm living star PI, (c) the selective replacement of the two chlorines of trichloromethylsilane with 3-arm star PI to form an H-shape intermediate, and (d) the replacement of the remaining chlorine of trichloromethylsilane by linear PI chains with double the molecular weight. All intermediate and final products were characterized via size exclusion chromatography, temperature gradient interaction chromatography and 1H-NMR spectroscopy. As expected, due to the inability to control the exact stoichiometry of the linking reactants, the main product (exact comb PI) is contaminated by a few by-products, despite the fact that anionic polymerization is the most efficient way to produce well-defined polymers. © 2013 The Royal Society of Chemistry.en
dc.description.sponsorshipKR is thankful to the Industrial Chemistry Laboratory of the University of Athens for providing guidance and laboratory facilities, as well as to the Marie-Curie DYNACOP (PITN-GA-2008-214627) project for financial support. TC acknowledges the supports from NRF (2008-0061892 and 2012R1A2A2A01015148).en
dc.publisherRoyal Society of Chemistryen
dc.titleSynthesis and characterization of an exact comb polyisoprene with three branches having the middle branch twice the molecular weight of the other two identical external branchesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalPolymer Chemistryen
dc.contributor.institutionSchool of Chemical Sciences, S. R. T. M. University, Nanded, 431606 MS, Indiaen
dc.contributor.institutionDepartment of Chemistry, University of Athens, Panepistimiopolis, Zografou, 15771 Athens, Greeceen
dc.contributor.institutionDivision of Advanced Materials Science, Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang 790-784, South Koreaen
dc.contributor.institutionInstitute of Electronic Structure and Laser, FORTH, Heraklion, 71110 Crete, Greeceen
dc.contributor.institutionDepartment of Materials Science and Technology, University of Crete, Heraklion, 71003 Crete, Greeceen
kaust.authorHadjichristidis, Nikolaosen
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