Synthesis of end-functionalized polymers by means of living anionic polymerization. 9. Synthesis of well-defined end-functionalized polymers with one, two, three, or four monosaccharide residues

Macromolecules

Volumn 31, Issue 7, 1998, Pages 2057-2063

  Hayashi, Mayumi ^a   Loykulnant, Surapich ^a   Hirao, Akira ^a   Nakahama, Seiichi ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

DERIVATIVES; LIGHT SCATTERING; METHANOL; MICELLES; OPTICAL VARIABLES MEASUREMENT; POLYISOPRENES; POLYSTYRENES; SYNTHESIS (CHEMICAL);

ANIONIC LIVING POLYMER; END FUNCTIONALIZED POLYMER; FRUCTOPYRANOSE; GALACTOPYRANOSE; GLUCOFURANOSE; MONOSACCHARIDE RESIDUE; SORBOFURANOSE;

ANIONIC POLYMERIZATION;

EID: 0032492555     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma9712357     Document Type: Article

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18. It is presumed that the dimers result from either a lithium-chloride exchange followed by the coupling between the chlorinated polystyrene thus generated and polystyryllithium or a single-electron transfer (SET) pathway followed by the coupling between the generated polymer radicals. Yields of dimers in our termination reactions are as follows: 5% in the reactions of polystyryllithium with 1 and polyisoprenyllithium with 2; 10% in the reactions of polystyryllithium with 3 and polyisoprenyllithium with 1, respectively. More complicately, the amount of dimer or even dimer formation is not reproducible in the same reaction. It was also observed under the conditions employed here that dimeric product was not always but often formed in yields of around 3% even by quenching with degassed methanol. This is possibly produced as a result of an elimination of LiH from the living polymer to afford the polymer with C=C end group, followed by the reaction with another living polymer to produce the dimeric product. Amounts of the dimers produced in the reactions should be therefore evaluated to take this into consideration.
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23. 1H NMR were 1.74 and 1.88, respectively. Furthermore, small amounts (ca. 3 wt %) of unfunctionalized polymers were always produced. Thus, 5 was not yet purified enough yet by this method. Poly(styryllithium) could be quantitatively end-functionalized by the use of 5 to which sec-BuLi of 10 mol % was further added.
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