Amine-terminal polystyrenes: A new strategy for synthesis and new methods for determination of functionality

Macromolecules

Volumn 31, Issue 12, 1998, Pages 3759-3763

  Cernohous, J J ^b   Macosko, C W ^a   Hoye, T R ^b  

^a University of Minnesota   (United States)

^b UNIVERSITY OF MINNESOTA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; ANIONIC POLYMERIZATION; CHLORINE COMPOUNDS; GEL PERMEATION CHROMATOGRAPHY; MOLECULAR WEIGHT DISTRIBUTION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SILANES; SYNTHESIS (CHEMICAL);

END CAPPING REACTION;

POLYSTYRENES;

EID: 0032098583     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma971142p     Document Type: Article

References (26)

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19. Unpublished observations of T. D. Jones.
20. No bimodal character to the GPC's was observed for polymer 3 synthesized in cyclohexane. However, when 1 was treated with less than 1 equiv of trapping agent 2, the formation of 2:1 adducts arising from subsequent displacement of the alkyl chloride was observed in the GPC.
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22. 5c (14) Alternatively, ∼2 kg/mol PEG-NPC is commercially available upon request (Shearwater). This reagent should be useful for determining the extent of amine incorporation in lower molecular weight polystyrenes (to ∼5 K).
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24. Both the homogenous and heterogeneous cross-coupling reaction between polymers bearing aliphatic amines and cyclic anhydrides is extremely fast in the melt. Reaction is essentially complete after very short mixing times (∼5 min at 200°C). These reactions can also be performed in solution (∼1 mM in THF), but reaction times are considerably longer (24 h at RT).
25. Each of the amino-functionalized PS polymers could be obtained in chromatographically pure form (i.e. f = 1.0) by simple column chromatography on silica gel by gradient elution with cyclohexane/ether (10:1, then 1:1 respectively) as the solvent (even in the case of 101 kg/mol of 5g). We have found this solvent gradient to be useful for purifying a variety of monofunctional polystyrenes.
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