Polystyrene-supported organotin dichloride as recyclable catalyst in lactone ring-opening polymerisation. Assessment by high resolution Magic Angle Spinning (hr-MAS) NMR
[en] Dialkyltin dichloride grafted to a cross-linked polystyrene, with the formula [PH](1-t)[P(CH2)nSnBuCl2]t (P=[CH2CH(pC6H4)], t=the degree of functionalization, and n=6 or 11), is investigated as a recyclable catalyst in the ring-opening polymerization (ROP) of e-caprolactone (CL). It is demonstrated that high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy is an invaluable tool to characterize completely the supported catalyst. The 2D 1H-13C HSQC HR-MAS spectrum, in particular, allowed extensive assignment of the 1H and 13C resonances, as well as accurate measurement of the nJ(1H-117/119Sn) and nJ(13C-117/119Sn) coupling constants. 1H and 119Sn HR-MAS NMR spectroscopy is presented as a monitoring tool for catalytic processes based on organotin compounds, particularly for the investigation of the extent to which polymerization residues are observable in situ in the material pores and for the assessment of the chemical integrity and recycling conditions of the grafted catalyst. From polymerization experiments with CL, initiated by n-propanol and with [PH](1-t)[P(CH2)nSnBuCl2]t of various compositions as the supported catalyst, it appears that a partial 'burst' of the polystyrene support occurs when the length of the alkyl spacer is limited to n=6, as a result of polymer chains growing within the pores of the support. However, extension of the length of the aliphatic polymethylene spacer from 6 to 11 carbon atoms preserves the support integrity and allows the production of catalyst-deprived poly(e-caprolactone) (PCL) oligomers. A preliminary attempt to recycle the heterogeneous catalyst has shown that very good reproducibility can be obtained, in terms of both catalyst activity and molecular-weight parameters of the as-recovered PCL polyester chains.
Disciplines :
Chemistry
Author, co-author :
Deshayes, Gaëlle
Poelmans, K.
Verbruggen, I.
Camacho-Camacho, C.
Degée, Philippe
Pinoie, V.
Martins, J.C.
Piotto, M.
Biesemans, M.
Willem, R.
Dubois, Philippe ; Université de Mons > Faculté des Sciences > Matériaux Polymères et Composites
Language :
English
Title :
Polystyrene-supported organotin dichloride as recyclable catalyst in lactone ring-opening polymerisation. Assessment by high resolution Magic Angle Spinning (hr-MAS) NMR
Publication date :
18 July 2005
Journal title :
Chemistry
ISSN :
0947-6539
Publisher :
John Wiley & Sons, United Kingdom
Volume :
11
Issue :
15
Pages :
4550-4559
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S816 - Matériaux Polymères et Composites
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
Commentary :
Publié en ligne le 18 juillet 2005
Lecture en ligne: http://onlinelibrary.wiley.com/doi/10.1002/chem.200500065/pdf
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