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The ceiling temperature of polystyrene with styryllithium headgroups is about 250°C, so that in living PS solutions at usual experimental temperatures all the monomers are incorporated and depolymerization is highly unlikely. A similar state of play exists for isoprenyllithium headgroups. Furthermore, isoprenyllithium headgroups are stable over a long life time. GPC measurements of terminated polymers showed no difference between samples drawn from freshly made living isoprenyllithium polymer solutions and those drawn from living polymer allowed to sit for three to four weeks before being terminated. Similar features have been observed for butadienyllithium headgroups. L. J. Fetters (private communication).
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In the literature, the term "living polymer" is also used to describe cylindrical micelles of short-chain or polymeric surfactants, which in equilibrium can change length. We will indeed discuss cylindrical micelles here, but will refer to them as such. Also, some living polymers, such as (poly)α-methylstyrene, can be observed at temperatures where the polymerization and depolymerization reactions are in equilibrium, so that the molecular weight distribution becomes broad (see Ref. 5 and references therein). That is not the case in the experiments of Ref. 4 (see previous note).
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Calculations of the point charges on the atoms of the aggregates depended on the method used; for small aggregates of methyllithium (tetramers, hexamers, and octomers), the semiempirical PM3 method found charges of approximately +0.25e on the lithium atoms and -0.3e to -0.45e on the carbons, with small charges on the hydrogens. More precise ab initio calculations with a 3-21G basis set found charges of +0.6e on the lithium atoms and - 1.0e on the carbons, with about +0.15e on the hydrogen atoms.
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0343961907
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DGAUSS 4.0, module in UNICHEM 4.1, Oxford Molecular (Oxford, England)
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DGAUSS 4.0, module in UNICHEM 4.1, Oxford Molecular (Oxford, England).
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42
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MOPAC V6.0, QCPE program 455, J. J. P. Stewart, 1990.
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0343961905
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CACHE V3.9, CACHE Scientific, Oxford Molecular (Oxford, England)
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CACHE V3.9, CACHE Scientific, Oxford Molecular (Oxford, England).
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47
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UNICHEM 4.1, Oxford Molecular (Oxford, England), the MNDO94 program with the PM3 Hamiltonian is based on MOPAC, see Ref. 42
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UNICHEM 4.1, Oxford Molecular (Oxford, England), the MNDO94 program with the PM3 Hamiltonian is based on MOPAC, see Ref. 42.
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