Solid‐supported well‐defined synthesis of telechelic polyester by acid‐promoted ring‐opening polymerization of ϵ‐caprolactone

Sudo, Atsushi; Endō, Takeshi

doi:10.1002/pola.10536

Cited by 3 publications

(1 citation statement)

References 10 publications

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“…After polymerization of CL, which was actually initiated by the grafted hydroxy functions, a-allyl, w-hydroxy PCL oligomers were isolated from the support by selective cleavage of the b-amino ester linker by using various halogenated alkyl and allyl derivatives. [10] The similarity between these strategies is the preliminary grafting of the true initiating species onto an insoluble support, which required both the PCL oligomers to be selectively untied from the support in order to isolate them, and the active centers to be regenerated prior to recycling the support.…”

Section: Introductionmentioning

confidence: 99%

Polystyrene‐Supported Organotin Dichloride as a Recyclable Catalyst in Lactone Ring‐Opening Polymerization: Assessment and Catalysis Monitoring by High‐Resolution Magic‐Angle‐Spinning NMR Spectroscopy

Deshayes

Poelmans

Verbruggen

et al. 2005

Chemistry A European J

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Dialkyltin dichloride grafted to a cross-linked polystyrene, with the formula [P-H]((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 epsilon-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 (n)J((1)H-(117/119)Sn) and (n)J((13)C-(117/119)Sn) 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 [P-H]((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(epsilon-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.

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Section: Introductionmentioning

confidence: 99%

Polystyrene‐Supported Organotin Dichloride as a Recyclable Catalyst in Lactone Ring‐Opening Polymerization: Assessment and Catalysis Monitoring by High‐Resolution Magic‐Angle‐Spinning NMR Spectroscopy

Deshayes

Poelmans

Verbruggen

et al. 2005

Chemistry A European J

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Monoaryloxo ytterbium(III) chlorides supported by β‐diketiminato ligands as novel initiators for the living ring‐opening polymerization of ε‐caprolactone

Xue¹,

Sun²,

Zhou³

et al. 2005

J. Polym. Sci. A Polym. Chem.

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Ring‐opening polymerization of ε‐caprolactone (ε‐CL) was carried out using β‐diketiminato‐supported monoaryloxo ytterbium chlorides L1Yb(OAr)Cl(THF) (1) [L1 = N,N′‐bis(2,6‐dimethylphenyl)‐2,4‐pentanediiminato, OAr = 2,6‐di‐tert‐butylphenoxo‐], and L2Yb(OAr′)Cl(THF) (2) [L2 = N,N′‐bis(2,6‐diisopropylphenyl)‐2,4‐pentanediiminato, OAr′ = 2,6‐di‐tert‐butyl‐4‐methylphenoxo‐], respectively, as single‐component initiator. The influence of reaction conditions, such as polymerization temperature, polymerization time, initiator, and initiator concentration, on the monomer conversion, molecular weight, and molecular weight distribution of the resulting polymers was investigated. Complex 1 was well characterized and its crystal structure was determined. Some features and kinetic behaviors of the CL polymerization initiated by these two complexes were studied. The polymerization rate is first order with respect to monomer. The Mn of the polymer increases linearly with the increase of the polymer yield, while polydispersity remained narrow and unchanged throughout the polymerization in a broad range of temperatures from 0 to 50 °C. The results indicated that the present system has a “living character”. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1147–1152, 2006

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Solid‐supported synthesis of well‐defined amphiphilic block copolymer from methacrylates

Nagai

Fujii

Ochiai

et al. 2008

J. Polym. Sci. A Polym. Chem.

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A new facile method for preparation of an amphiphilic block copolymer via a one‐pot sequential atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) and 2‐hydroxyethyl methacrylate (HEMA) on solid support was developed. As a model homopolymerization for the solid‐supported block copolymerization, ATRPs of MMA and HEMA in toluene and in 2‐butanone/1‐propanol solvent system were carried out, respectively. Crosslinked polystyrene beads bearing 2‐bromoisobutyrate moieties successfully initiated the polymerizations of MMA and HEMA in controlled manner. On the basis of the successful results, the one‐pot synthesis of amphiphilic block copolymer by changing the reaction medium was performed. After the ATRP of MMA in toluene at 90 °C for 1 h, the poly(MMA) formed on the beads were washed by continuous flow of 2‐butanone/1‐propanol under nitrogen with the aid of a glass filter in a U‐shaped glass vessel. Then, 2‐butanone/1‐propanol, copper chloride (I), 2,2′‐bipyridyl, and HEMA were added and heated at 50 °C for 48 h with shaking the vessel, followed by treatment with trifluoroacetic acid to isolate the well‐defined amphiphilic block copolymer, poly(MMA‐b‐HEMA). These demonstrated the feasibility of the present strategy for well‐defined synthesis of amphiphilic block copolymers via a one‐pot procedure. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1990–1997, 2008

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Solid‐supported well‐defined synthesis of telechelic polyester by acid‐promoted ring‐opening polymerization of ϵ‐caprolactone

Cited by 3 publications

References 10 publications

Polystyrene‐Supported Organotin Dichloride as a Recyclable Catalyst in Lactone Ring‐Opening Polymerization: Assessment and Catalysis Monitoring by High‐Resolution Magic‐Angle‐Spinning NMR Spectroscopy

Polystyrene‐Supported Organotin Dichloride as a Recyclable Catalyst in Lactone Ring‐Opening Polymerization: Assessment and Catalysis Monitoring by High‐Resolution Magic‐Angle‐Spinning NMR Spectroscopy

Monoaryloxo ytterbium(III) chlorides supported by β‐diketiminato ligands as novel initiators for the living ring‐opening polymerization of ε‐caprolactone

Solid‐supported synthesis of well‐defined amphiphilic block copolymer from methacrylates

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