Kinetics study of Ti[O(CH2)4OCHCH2]4 initiated ring‐opening polymerization of ε‐caprolactone by differential scanning calorimetry

Li, Peichun; Zerroukhi, Amar; Chen, Jianding; Chalamet, Yvan; Jeanmaire, Thomas; Xia, Zhean

doi:10.1002/app.28962

Cited by 18 publications

(20 citation statements)

References 20 publications

(29 reference statements)

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“…Amongst these, titanium alkoxides, Ti(OR) 4 , have attracted increasing attention due to their high activity and low toxicity [11,14,15,[17][18][19].…”

Section: Introductionmentioning

confidence: 99%

“…The kinetics of the ROP of ε-CL have been studied by various techniques such as gravimetry [17], dilatometry [11,22], and differential scanning calorimetry (DSC) [14,23]. The DSC technique has been used extensively to evaluate kinetic parameters such as the activation energy with varying fraction of conversion.…”

Section: Introductionmentioning

confidence: 99%

“…A variety of catalysts and initiators have recently been reported for use in the ROP of ε-CL such as Brönsted acids [7,8] and various metal complexes [9] of Al [10], Sn [11], Zn [12], Ln [13] and Ti [14][15][16]. Amongst these, titanium alkoxides, Ti(OR) 4 , have attracted increasing attention due to their high activity and low toxicity [11,14,15,[17][18][19].…”

Section: Introductionmentioning

confidence: 99%

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Isoconversional kinetic analysis of ring-opening polymerization of ε-caprolactone: Steric influence of titanium(IV) alkoxides as initiators

et al. 2012

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Four titanium(IV) alkoxides, namely: Ti(IV) npropoxide (1), Ti(IV) n-butoxide (2), Ti(IV) tert-butoxide (3), and Ti(IV) 2-ethylhexoxide (4), have been used as initiators in the bulk ring-opening polymerization (ROP) of ε-caprolactone (ε-CL). The influence of the alkoxide group on the course of the ROP of ε-CL was investigated by means of 1 H-NMR and differential scanning calorimetry (DSC). The 1 H-NMR spectra confirmed that the ROP reaction of ε-CL proceeded via the widely accepted coordinationinsertion mechanism for each of the four initiators. Isoconversional methods have been used to evaluate non-isothermal DSC data via the equations of Friedman, Kissinger-AkahiraSunose (KAS) and Ozawa-Flynn-Wall (OFW). The kinetic studies showed that the polymerization rate for the four initiators (1-4) was in the order of 1>2≈4>3. The lowest activation energies (40-47, 42-44, and 49-52 kJ/mol for the Friedman, KAS and OFW methods respectively) were found in the polymerizations using Ti(IV) n-propoxide (1), while the highest activation energies (84-107, 77-87, and 80-91 kJ/mol for the Friedman, KAS and OFW methods respectively) were obtained using Ti(IV) tert-butoxide (3). Differences in the rates of polymerization and the activation energies amongst the four initiators appeared to be governed mainly by the different degrees of steric hindrance in the initiator structure. These results represent important findings regarding the steric influence of the alkoxide groups on the kinetics of the ROP of ε-CL initiated by titanium(IV) alkoxides.

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“…Amongst these, titanium alkoxides, Ti(OR) 4 , have attracted increasing attention due to their high activity and low toxicity [11,14,15,[17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Isoconversional kinetic analysis of ring-opening polymerization of ε-caprolactone: Steric influence of titanium(IV) alkoxides as initiators

et al. 2012

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“…The kinetic parameters determined from nonisothermal DSC polymerization of ε-CL initiated by Al(OsecBu) 3 Table I. The results show the increment of T m with increasing heating rate, which is generally occurred in the DSC experiment [13,26].…”

Section: Nonisothermal and Isothermal Dsc Measurementsmentioning

confidence: 97%

“…The DSC technique is frequently used to study the kinetics of the polymerization process [9,13,26,27]. It is accepted that this technique is fast to study the kinetics of polymerization reactions [9,13].…”

Section: Introductionmentioning

confidence: 99%

DSC Kinetics Analysis for the Synthesis of Three‐Arms Poly(ε‐caprolactone) Using Aluminum Tri‐sec‐Butoxide as Initiator

Limwanich

Punyodom

Kungwan

et al. 2015

Int J of Chemical Kinetics

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The kinetics of the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) initiated by soluble aluminum tri-sec-butoxide (Al(OsecBu) 3 ) has been investigated by the differential scanning calorimetry (DSC). The DSC polymerizations were carried out under nonisothermal and isothermal conditions to obtain three-arms poly(ε-caprolactone) (PCL). From nonisothermal DSC, the polymerization rate (dα/dt) increased with increasing heating rates. The values of E a were determined from Kissinger (63 ± 2 kJ mol −1 ), Friedman (31.0 -63.0 kJ mol −1 ), and Starink (64.0 -71.0 kJ mol −1 ) methods. From isothermal DSC, the dα/dt and the apparent rate constant (k app ) increased with increasing polymerization temperatures. The ROP of ε-CL initiated by Al(OsecBu) 3 occurred via the coordination insertion mechanism. The number average molecular weight (M n ) and percent yield of the synthesized PCL was enhanced by increasing polymerization temperature. The synthesized PCL withM n of 2.4 × 10 4 was obtained using a molar ratio of monomer to Al-O active center ([M]/[Al-O]) of 400 at 150ºC for 24 h. Al(OsecBu) 3 is one of the promising initiator due to its solubility, low transesterification reaction, and high efficiency in ε-CL polymerization. C 2015 Wiley Periodicals, Inc. Int J Chem Kinet 47: [734][735][736][737][738][739][740][741][742][743] 2015

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Synthesis of poly(ϵ‐caprolactone)‐block‐poly(n‐butyl acrylate) by the combination of ring‐opening polymerization and atom transfer radical polymerization with Ti[OCH₂CCl₃]₄ as a difunctional initiator. II. Synthesis and characterization of poly(ϵ‐caprolactone)‐block‐poly(n‐butyl acrylate) copolymers

Xia

Zerroukhi

et al. 2009

J of Applied Polymer Sci

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ABSTRACT:The kinetics and controllability of the Ti[OCH 2 CCl 3 ] 4 -initiated atom transfer radical polymerization (ATRP) of n-butyl acrylate were investigated. Then, with Ti[OCH 2 CCl 3 ] 4 as the initiator, poly(e-caprolactone)-block-poly(n-butyl acrylate) (PCL-b-PBA) copolymers were synthesized by the combination of the ring-opening polymerization (ROP) of e-caprolactone and ATRP of n-butyl acrylate. With different sequential combinations of ROP and ATRP, three routes were used to synthesize PCL-b-PBA copolymers. The composition characterization results demonstrated that the first-ROP-then-ATRP route was most efficient; it was followed by the in situ ATRP and ROP route and then the first-ATRP-then-ROP route. Furthermore, with a Haake Rheomix reactor (Thermo Electron Corp., Karlsruhe, Germany), the PCL-b-PBA copolymers were in situ synthesized in a poly(methyl methacrylate) matrix.

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Kinetics study of Ti[O(CH₂)₄OCHCH₂]₄ initiated ring‐opening polymerization of ε‐caprolactone by differential scanning calorimetry

Cited by 18 publications

References 20 publications

Isoconversional kinetic analysis of ring-opening polymerization of ε-caprolactone: Steric influence of titanium(IV) alkoxides as initiators

Isoconversional kinetic analysis of ring-opening polymerization of ε-caprolactone: Steric influence of titanium(IV) alkoxides as initiators

DSC Kinetics Analysis for the Synthesis of Three‐Arms Poly(ε‐caprolactone) Using Aluminum Tri‐sec‐Butoxide as Initiator

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