Characterization of poly(ethylene glycol)-b-poly(ε-caprolactone) by liquid chromatography under critical conditions: Influence of catalysts and reaction conditions on product composition

Ahmed, Hasnat; Trathnigg, Bernd; Kappe, C. Oliver; Saf, Robert

doi:10.1016/j.eurpolymj.2009.05.001

Cited by 19 publications

(15 citation statements)

References 28 publications

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“…The established critical point of PCL in this study has never been reported. The advantage of the current critical conditions is an extended range of PCL molar mass compared to already reported critical conditions of PCL in aqueous mobile phase due to better solubility of higher molar mass PCL and higher pore size of the stationary phase , in line with the findings of Zorn et al . Such separation zone could be valuable for characterization of PCL‐containing block copolymers, polymer blends, and telechelic polymers, with an extended molar mass range.…”

Section: Resultssupporting

confidence: 71%

“…The synthesis of di‐ and tri‐block copolymers is conventionally performed by ring‐opening polymerization of ε‐caprolactone utilizing PEGs and Methoxy poly(ethylene glycol) (MeO‐PEGs) as macro‐initiator and stannous octoate as a catalyst . SEC is widely used for the determination of molecular weight and molecular weight distribution of synthetic polymers .…”

Section: Introductionmentioning

confidence: 99%

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Chromatographic characterization of amphiphilic di‐ and tri‐block copolymers of poly(ethylene oxide) and poly(ε‐caprolactone)

Irfan

Bhayo

Musharraf

et al. 2018

J of Separation Science

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Amphiphilic di- and tri-block copolymers based on poly(ethylene oxide) as a hydrophilic segment and poly(ε-caprolactone) as a hydrophobic part are synthesized by the ring-opening polymerization of ε-caprolactone while using poly(ethylene glycol)s and methoxy poly(ethylene glycol)s of varying molar masses as macro-initiators. The synthesized block copolymers are characterized with respect to their total relative molar mass and its distribution by size exclusion chromatography. Liquid chromatography at critical conditions of both blocks is established for the analysis of individual block lengths and tracking presence of unwanted homopolymers of both types in the block copolymer samples. New critical conditions of polycaprolactone on reversed phase column are reported using organic mobile phase. The established critical conditions of polycaprolactone extended the applicable molar mass range significantly compared to already reported critical conditions of polycaprolactone in aqueous mobile phase. Block copolymers are also analyzed at critical conditions of poly(ethylene glycol). Complete analysis of the di- and tri-block copolymers at corresponding critical conditions provided a fair estimate of molar mass of non-critical block besides information regarding presence of homopolymers of both types in the samples.

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Section: Resultssupporting

confidence: 71%

Section: Introductionmentioning

confidence: 99%

Chromatographic characterization of amphiphilic di‐ and tri‐block copolymers of poly(ethylene oxide) and poly(ε‐caprolactone)

Irfan

Bhayo

Musharraf

et al. 2018

J of Separation Science

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“…The authors report a degree of polymerization (DP) for PCL in the range of 3-24 and a degree of substitution (DS) of PVA from 0.35 to 0.89 and specify that both values were enhanced by microwave heating: irradiation was carried out at three power levels (340, 510 and 680 W), finding that the higher power provided higher DPs and DSs (Yu & Liu, 2007). Amphiphilic di-block PEG-b-PCL copolymers were synthesized in a one pot procedure under microwave irradiation using PEG monomethyl ester as oxydrilic initiator and boron trufluoride, Sodium hydride or stannous octoate as alternative catalysts, the latter yielding polymers with the highest purity (Ahmed et al, 2009). By means of a similar procedure, different authors obtained PEG-b-PCL copolymers with M w values ranging from 5,800 g/mol to 14,500 g/mol and very low polydispersity indexes (≤ 1.19).…”

Section: Poly(ε-caprolactone) Copolymersmentioning

confidence: 99%

Synthesis and processing of biodegradable and bio-based polymers by microwave irradiation

Frediani¹,

Giachi²,

Rosi³

et al. 2011

Microwave Heating

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“…1D), the presence of a second series of oligomers, likewise, spaced by m/z 114 (i.e., m/z 1051.6 and 1165.6) and separated from the homolog peaks of the main series by m/z 104. It was attributed to PCL (Table 1) formally corresponding to a loss of the diethylenglycol unit from PCLD polymer and they were identified as PCL cyclic oligomers [21][22][23][24], previously reported as a possible degradation pathway of PCL (Fig. 1) [25].…”

Section: Maldi Mass Spectra Of Polymer Sectionsmentioning

confidence: 84%

Using MALDI-TOF MS imaging and LC-HRMS for the investigation of the degradation of polycaprolactone diol exposed to different wastewater treatments

et al. 2017

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Polymers are used in high amounts in a wide range of applications from biomedicine to industry. Because of the growing awareness of the increasing amounts of plastic wastes in the aquatic environment during recent years, the evaluation of their biodegradability deserves special attention. In the past, most efforts were dedicated to studying the biodegradation of polyesters in soil and compost, while very little research has been conducted on their fate in wastewater. Here, we assessed the ability of bacterial communities residing in the aerobic and denitrification tank from a wastewater treatment plant (WWTP) to degrade the polymeric ester polycaprolactone diol (PCLD; average molecular weight of 1250 Da). Following the incubation of the solid polymer in WWTP tanks, matrixassisted laser desorption/ionization-mass spectrometry imaging (MALDI-MSI) was used to provide evidence for hydrolytic reactions and to study differences in the spatial degradation on the PCLD surface. It was demonstrated that regardless of the wastewater type, the chemical structure on the PCLD surface underwent modifications after 7 days of exposure.Apart from the parent PCLD peak series in MALDI-MSI mass spectra, the presence of a second oligomer series with mass peaks spaced by m/z 114 (as in PCLD) was observed. It was proposed to correspond to polycaprolactone (PCL) originating from the hydrolytic cleavage of the diethylene glycol from PCLD. Their ion masses were detected at m/z 104 below the PCLD peaks and their structures were proposed as PCL cyclized oligomers. Differences in the spatial distribution of low MW ions (<800) between the aerobic and denitrifying exposed samples in MALDI MSI were also noticeable. While the ions at m/z 221.1, 247.1 and 449.2 predominated in the aerobic exposed sample, those at m/z 475.5 and 677.4 were characteristic of the denitrifying one. The MALDI-MSI measurements in the low mass range were complemented with LC-HRMS analysis to determine plausible structures of the major degradation products. Ten transformation products (TPs) were detected in the denitrifying wastewater experiment, five of them were the result of ester hydrolysis forming caprolactone oligomers (TPs 220, 334, 448, 562, and 676) while the other series corresponded to formation of PCL chain with a terminal diethylene glycol, likewise formed by ester hydrolysis (TPs 246, 360, 474, 588, and 702).

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Characterization of poly(ethylene glycol)-b-poly(ε-caprolactone) by liquid chromatography under critical conditions: Influence of catalysts and reaction conditions on product composition

Cited by 19 publications

References 28 publications

Chromatographic characterization of amphiphilic di‐ and tri‐block copolymers of poly(ethylene oxide) and poly(ε‐caprolactone)

Chromatographic characterization of amphiphilic di‐ and tri‐block copolymers of poly(ethylene oxide) and poly(ε‐caprolactone)

Synthesis and processing of biodegradable and bio-based polymers by microwave irradiation

Using MALDI-TOF MS imaging and LC-HRMS for the investigation of the degradation of polycaprolactone diol exposed to different wastewater treatments

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