Kinetics and mechanism of cyclic esters polymerisation initiated with tin(II) octoate, 4. Influence of proton trapping agents on the kinetics of -caprolactone and L,L-dilactide polymerisation

Majerska, Katarzyna; Duda, Andrzej; Penczek, Stanisław

doi:10.1002/1521-3927(20001201)21:18<1327::aid-marc1327>3.3.co;2-0

Cited by 27 publications

(44 citation statements)

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“…Note that at high monomer conversions and high polymerization temperatures (i.e., higher than 130 °C), scission and trans‐esterification reactions become important, resulting in a decrease of

{\overset{true‾}{M}}_{normalw}

and an increase of polydispersity index. On the other hand, at low polymerization temperatures, their contribution to the molecular weight developments is not significant . The experimentally measured values of the polydispersity index (i.e.,

{\overset{true‾}{M}}_{normalw} / {\overset{true‾}{M}}_{normaln}

) varied from 1.0 to 2.6.…”

Section: Resultsmentioning

confidence: 93%

“…However, the most controversial reaction step regards the initiation step. The two initiation mechanisms that have prevailed in the literature, are the “monomer activated mechanism” and the “alkoxide initiation mechanism” . The former mechanism involves the polarization of the L , L ‐lactide carbonyl bond via its interaction with stannous octoate and a proton, resulting in the formation of a carbocation and a cyclic intermediate that initiates the polymerization.…”

Section: Introductionmentioning

confidence: 99%

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An Experimental and Theoretical Investigation of the Ring‐Opening Polymerization of L,L‐Lactide

Pladis

Karidi

Mantourlias

et al. 2014

Macro Reaction Engineering

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A comprehensive mathematical model was developed based on a detailed kinetic mechanism to predict the dynamic evolution of monomer conversion and molecular weight averages. The predictive capabilities of the mathematical model are demonstrated by a direct comparison of model predictions with literature and new experimental data on monomer conversion as well as number and weight average molecular-weight of PLLA. The effects of monomer to initiator molar ratio and polymerization temperature on the polymerization rate and average molecular weight properties of polylactide were experimentally determined and compared with model predictions. For this reason, high molecular weight polylactides were synthesized in melt via the ring-opening polymerization of L,Llactide, in the presence of stannous octoate.

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{\overset{true‾}{M}}_{normalw}

{\overset{true‾}{M}}_{normalw} / {\overset{true‾}{M}}_{normaln}

) varied from 1.0 to 2.6.…”

Section: Resultsmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

An Experimental and Theoretical Investigation of the Ring‐Opening Polymerization of L,L‐Lactide

Pladis

Karidi

Mantourlias

et al. 2014

Macro Reaction Engineering

View full text Add to dashboard Cite

show abstract

“…The modifying hydrophilicity, degradability, and breaking elongation of PLA were reviewed [3][4][5]. To do this, modifying the bulk and surface of PLA by introducing hydrophilic and biocompatible components and by adjusting the surface energy, surface charge, and surface roughness were described [4][5][6][7][8].…”

Section: Introductionmentioning

confidence: 99%

Polylactic acid (PLA) synthesis and modifications: a review

et al. 2009

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“…In-situ addition of probe molecules to reactant stream during reaction can provide useful information about reaction 45 mechanism, and the probe molecule technique has been widely adopted in heterogeneous catalysis studies [16][17][18] . A great deal of effort has been made to reveal the HAS mechanism by probe molecule technique [19][20][21][22][23] .…”

Section: Introductionmentioning

confidence: 99%

Elucidation of reaction network of higher alcohol synthesis over modified FT catalysts by probe molecule experiments

Yang

Wang

Xiao

et al. 2015

Catal. Sci. Technol.

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The reaction network of high alcohol synthesis over a CuFe/ZrO 2 modified FT catalyst was investigated by probe molecule technique, and the influence of various probe molecules (alkane, alcohol, aldehyde and olefin) on catalytic performance was evaluated in detail. Alcohol selectivity and CO conversion remain almost constant when alkane was used as the probe molecule. However, the products shift to higher carbon number significantly due to the alleviation of the retention of heavy products by the extraction of 10 the added alkane. When alcohol was introduced into the reaction system, a considerable amount of esters with unique structures were formed with the formula of RCO 2 R', where R' is the alkyl group from the added alcohols, and such esters followed ASF distribution with similar chain propagation factor as that of the corresponding higher alcohols. With the addition of aldehyde as probe molecule, most of the added aldehyde was directly hydrogenated to the corresponding alcohol, but a considerable amount of esters 15 were also detected in the reaction products, which could be attributed to the reaction between the surface acyls adsorbed from introduced aldehydes molecules and the alcohols synthesized by syngas. The added 1-olefins were directly hydrogenated to the corresponding paraffins, incorporated into growing carbon chain to form higher products or transformed into alcohol with one more carbon number by CO insertion reaction. Based on these results, the catalytic mechanism and reaction network of higher alcohol synthesis 20 over modified FT catalyst were discussed.

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Kinetics and mechanism of cyclic esters polymerisation initiated with tin(II) octoate, 4. Influence of proton trapping agents on the kinetics of -caprolactone and L,L-dilactide polymerisation

Cited by 27 publications

References 0 publications

An Experimental and Theoretical Investigation of the Ring‐Opening Polymerization of L,L‐Lactide

An Experimental and Theoretical Investigation of the Ring‐Opening Polymerization of L,L‐Lactide

Polylactic acid (PLA) synthesis and modifications: a review

Elucidation of reaction network of higher alcohol synthesis over modified FT catalysts by probe molecule experiments

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