The thermodynamics of ϵ-caprolactone, its polymer and of ε-caprolactone polymerization in the 0–350°K range

Yevstropov, A.A.; Lebedev, N.K.; Karpova, Ye.A.; Lyudvig, Ye.B.; Belen'kaya, B.G.

doi:10.1016/0032-3950(78)90388-x

Cited by 12 publications

(7 citation statements)

References 11 publications

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“…The Δ H m value for PCL is 4.3 kJ · mol −1 . The calculated values of Δ H m of PLLA and PCL are lower than the values measured by others:27, 30 13.4 and 16.4 kJ · mol −1 , respectively.…”

Section: Resultscontrasting

confidence: 74%

AB₂ Functional Polyesters via Ring Opening Polymerization: Synthesis and Characterization

Velthoen

Dijkstra

Feijén

2009

Macro Chemistry & Physics

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Aliphatic AB2 functional polyesters were conveniently prepared by the ring opening polymerization of ε‐caprolactone and L‐lactide in the presence of the AB2 functional initiator 2,2‐bis(hydroxymethyl)propionic acid (bis‐MPA) and Sn(Oct)2 as the catalyst. In L‐lactide polymerization, both bis‐MPA hydroxyl groups initiated the polymerization reaction, but for ε‐caprolactone polymerization this depended on the monomer to initiator to catalyst ratio. Initiation at two hydroxyl groups occurred at high monomer to initiator ([M]/[I]) ratio and at high Sn(Oct)2 to monomer ratio. The melting temperatures of the AB2‐functional PLLA and PCL polymers were comparable to linear polymers with a $\overline {DP}$ equal to the $\overline {DP}$ per arm in the polymer.

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Section: Resultscontrasting

confidence: 74%

AB₂ Functional Polyesters via Ring Opening Polymerization: Synthesis and Characterization

Velthoen

Dijkstra

Feijén

2009

Macro Chemistry & Physics

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“…As expected, the polymerization of MDO is characterized by a typical entropy of polymerization for this type of monomer (-42 J mol -1 K -1 ) and a modest enthalpy of polymerization (-12 kJ mol -1 ). Comparison of these values, in particular ∆H p 0 , to those of several structurally related monomers (Table 4) 48,[51][52][53] confirms our prediction of a less favorable equilibrium constant for polymerization of MDO. The negative value of ∆H p 0 for the polymerization of MDO indicates that there is a "ceiling temperature" (T c ) at which [MDO] e ) [MDO] 0 and above which polymerization will not take place (at prevented polymerizations below -30 °C, on the basis of the preliminary polymerization kinetics at this temperature (equilibrium was reached within 1 h), we believe that the yttrium system used in this work would be reasonably active at even lower temperatures.…”

Section: T Gsupporting

confidence: 80%

Perfectly Alternating Copolymer of Lactic Acid and Ethylene Oxide as a Plasticizing Agent for Polylactide

2001

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The ring-opening polymerization of 3-methyl-1,4-dioxan-2-one (MDO) mediated by a catalytic system composed of Y[N(TMS)2]3 and benzyl alcohol (BnOH) led to a new polymer (PMDO) comprised of perfectly alternating lactic acid and ethylene oxide repeat units. Samples of PMDO were characterized by NMR spectroscopy, size exclusion chromatography (SEC), and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS). In a series of MDO polymerizations ([MDO]0 ) 3.0 M in toluene, between -30 and 60°C), the equilibrium monomer concentrations were measured. The thermodynamic parameters for the polymerization reaction were determined: ∆Hp°) -12.1 ( 0.5 kJ mol -1 and ∆Sp°) -42 ( 2 J mol -1 K -1 . The glass transition temperature (Tg) of PMDO was determined to be ≈-24°C by differential scanning calorimetry and found to vary little over the molecular weight range studied (3-21 kg/mol). Mixtures of low-molecular-weight PMDO and atactic polylactide (PLA) were prepared by solution casting and subsequent annealing significantly above the Tg's of the individual components. Miscibility of PLA and PMDO was evinced by single Tg's that were well-described by the Fox relationship for miscible blends. Because of its miscibility with PLA and low Tg, PMDO has potential as a macromolecular plasticizing agent for commercially relevant PLA.

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“…Moreover, in polymerizations initiated with A4, Mn is reduced after [eCL] reaches its equilibrium concentration and the reaction mixture is maintained at the monomer ^living polymer cyclic oligomer equilibrium (Figure 7). The equilibrium monomer concentration ([eCiJeq) is equal to 5 x 10-3 mol-L-1 at 25 °C, as calculated from the thermodynamic data given in ref 30. At these conditions, the unreacted A4 molecules initiate polymerization with monomer and cyclic oligomers present at equilibrium, longer chains depropagate, and new chains are formed at their expense.…”

Section: Resultsmentioning

confidence: 99%

Polymerization of .epsilon.-Caprolactone Initiated by Aluminum Isopropoxide Trimer and/or Tetramer

Duda¹,

Penczek²

1995

Macromolecules

157

136

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The thermodynamics of ϵ-caprolactone, its polymer and of ε-caprolactone polymerization in the 0–350°K range

Cited by 12 publications

References 11 publications

AB₂ Functional Polyesters via Ring Opening Polymerization: Synthesis and Characterization

AB₂ Functional Polyesters via Ring Opening Polymerization: Synthesis and Characterization

Perfectly Alternating Copolymer of Lactic Acid and Ethylene Oxide as a Plasticizing Agent for Polylactide

Polymerization of .epsilon.-Caprolactone Initiated by Aluminum Isopropoxide Trimer and/or Tetramer

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The thermodynamics of ϵ-caprolactone, its polymer and of ε-caprolactone polymerization in the 0–350°K range

Cited by 12 publications

References 11 publications

AB2 Functional Polyesters via Ring Opening Polymerization: Synthesis and Characterization

AB2 Functional Polyesters via Ring Opening Polymerization: Synthesis and Characterization

Perfectly Alternating Copolymer of Lactic Acid and Ethylene Oxide as a Plasticizing Agent for Polylactide

Polymerization of .epsilon.-Caprolactone Initiated by Aluminum Isopropoxide Trimer and/or Tetramer

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Product

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About

AB₂ Functional Polyesters via Ring Opening Polymerization: Synthesis and Characterization

AB₂ Functional Polyesters via Ring Opening Polymerization: Synthesis and Characterization