Ring‐opening polymerization of 1,4‐dioxan‐2‐one initiated by lanthanum isopropoxide in bulk

Zhu, Xiaolan; Wu, Gang; Qiu, Zhi-Cheng; Gong, Jie; Yang, Ke‐Ke; Wang, Yu‐Zhong

doi:10.1002/pola.22849

Cited by 16 publications

(24 citation statements)

References 75 publications

(93 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…ROPs of lactone41 and lactide37, 45 initiated by titanium alkoxides occur via a coordination‐insertion mechanism. This mechanism was proved to exist in the ROP of PDO initiated by Al(O i Pr) 3 20 and La(O i Pr) 3 33. Therefore, it is reasonable to suppose that the coordination‐insertion mechanism operates in the ROP of PDO initiated by titanium alkoxides in this study.…”

Section: Resultsmentioning

confidence: 65%

“…When ROP of PDO was initiated by Al(O i Pr) 3 20 and La(O i Pr) 3 ,33 there were only 1.3 effective alkoxides in both cases, which indicated that not all the three O i Pr groups are able to initiate the ROP of PDO. In this study, we have also estimated the effective alkoxide initiation sites of the individual titanium alkoxides.…”

Section: Resultsmentioning

confidence: 96%

“…It has been revealed that the ROP of ε‐caprolactone,35, 36 lactide,38 and cyclic carbonates39, 40 initiated by titanium alkoxides occurs via the cleavage of acyl–oxygen bond. In addition, the ROP of 1,4‐dioxan‐2‐one initiated by Al(O i Pr) 3 20 and La(O i Pr) 3 33 also occurs with cleavage of acyl–oxygen bonds.…”

Section: Resultsmentioning

confidence: 99%

“…In addition, zinc lactate (Zn(Lac) 2 ),21 enzymes,5 and lanthanum isopropoxide (La(O i Pr) 3 )33 have also been reported to initiate the ROP of 1,4‐diaxon‐2‐one. However, problems have been encountered when using these initiators, for example, low ultimate conversion of monomer (86%) with La(O i Pr) 3 as a catalyst,33 low activity of Zn(Lac) 2 and enzymes, to mention a few. Thus, new initiators with high activity and efficiency are still desirable for the efficient mass production of PPDO.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Rapid ring‐opening polymerization of 1,4‐dioxan‐2‐one initiated by titanium alkoxides

Zeng

Srinivansan

et al. 2010

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

Ring-opening polymerization of 1,4-dioxan-2-one in bulk was initiated by three titanium alkoxides, titanium dichlorodiisopropoxide (TiCl 2 (OiPr) 2 ), titanium chlorotriisopropoxide (TiCl(OiPr) 3 ), and titanium tetraisopropoxide (Ti(OiPr) 4 ). The results indicate that the polymerization rate increased with number of OiPr groups in the initiator. High conversion of monomer (90%) and high molecular weight (11.9 Â 10 4 g/mol) of resulting polymer can be achieved in only 5 min at 60 C with Ti(OiPr) 4 as an initiator. Analysis on nuclear magnetic resonance (NMR) spectra suggests the initiating sites for TiCl 2 (OiPr) 2 , TiCl(OiPr) 3 , and Ti(OiPr) 4 to be 1.9, 2.6, and 3.8, respectively. Coordinationinsertion mechanism for the polymerization via cleavage of the acyl-oxygen bonds of the monomer was proved by NMR investigation. Kinetic studies indicate that polymerization initiated by Ti(OiPr) 4 followed a first-order kinetics, with an apparent activation energy of 33.7 kJ/mol. It is noteworthy that this value is significantly lower than earlier reported values with other catalysts, namely La(OiPr) 3 (50.5 kJ/mol) and Sn(Oct) 2 (71.8 kJ/mol), which makes it an attractive catalyst for reactive extrusion polymerization. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: [5885][5886][5887][5888][5889][5890] 2010

show abstract

Section: Resultsmentioning

confidence: 65%

Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Rapid ring‐opening polymerization of 1,4‐dioxan‐2‐one initiated by titanium alkoxides

Zeng

Srinivansan

et al. 2010

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

show abstract

“…17,18 Furthermore, PPDO has proven to be tougher than PLA and even high-density polyethylene with a tensile strength of approximately 7000 psi for an ultimate elongation ranging from 500% to 600%. [21][22][23][24][25][26] Because PPDO has potential applications in the biomedical and pharmaceutical industries either as biodegradable implants or in controlled drug-delivery systems, it is necessary to remove all the traces of the metallic residues. 20 In general, PPDO can be synthesized by the ring-opening polymerization (ROP) of p-dioxanone (PDO) using metallic catalysts such as tin(II) bis(2-ethylhexanic acid), triethylaluminum, aluminum alkoxides, zinc derivatives, ferric alkoxides, titanium alkoxides, and yttrium complexes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of metal‐free poly(p‐dioxanone) by phosphazene base catalyzed ring‐opening polymerization

Yang

Bai

Xue

et al. 2015

J of Applied Polymer Sci

View full text Add to dashboard Cite

Poly(p-dioxanone) (PPDO) has received significant attention due to its good biocompatibility and fast biodegradation profiles. In addition, PPDO is a polymer with high potential in biomedical applications. However, the conventional syntheses of PPDO via the ring-opening polymerization (ROP) of p-dioxanone (PDO) often use a metallic catalyst, which significantly limits its biorelated applications. This investigation was focused on the synthesis of metal-free PPDO by using phosphazene base t-BuP 4 as the catalyst. The effects of the reaction conditions including temperature, reaction time, initiators, and feed molar ratios were studied in detail by nuclear magnetic resonance spectroscopy, viscosimetry, differential scanning calorimetry, and thermogravimetric analysis. The results showed that t-BuP 4 exhibited especially high activity in catalyzing alcohol or aniline to initiate the ROP of PDO, consequently resulting in metal-free PPDOs. The polymerization was optimum at a reaction temperature of approximately 1008C and 88.7% of PDO was consumed. The viscosity-average molecular weights of the resulting polymer reached as high as 2.09 3 10 4 g/mol. The molar ratios of [PDO]/[t-BuP 4 ] also had an obvious effect on both the polymerization and the resulting polymer. Increasing [PDO]/[t-BuP 4 ] ratios facilitated the molecular weight growth, whereas the conversions of PDO significantly decreased. V C 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43030.

show abstract

The influence of coexisted monomer on thermal, mechanical, and hydrolytic properties of poly(p‐dioxanone)

Zhou

Wen

et al. 2016

J of Applied Polymer Sci

View full text Add to dashboard Cite

Poly(p‐dioxanone) (PPDO), a typical aliphatic poly(ether‐ester), is generally synthesized via ring‐opening polymerization of 1,4‐dioxan‐2‐one (p‐dioxanone, PDO) monomer. However, a quite amount of PDO monomer should coexist with PPDO product due to the characteristics of the equilibrium polymerization. To clarify the effects of PDO on the properties of PPDO, a series of PPDO/PDO mixtures with different PDO content were prepared by adding PDO to pure PPDO. The thermal, mechanical, and hydrolytic properties of PPDO and PPDO/PDO mixtures were investigated systematically. It reveals that the existence of PDO in the polymer can act as plasticizer to facilitate the crystallization of PPDO, but the increasing of PDO content deteriorates the mechanical properties of the polymers, especially when the PDO loading is more than 3 php. The PDO does not distinctly affect PPDO thermal decomposition, but obviously accelerates the PPDO hydrolytic degradation. This work may provide an important reference for the industrialization and application of PPDO. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43483.

show abstract

Ring‐opening polymerization of 1,4‐dioxan‐2‐one initiated by lanthanum isopropoxide in bulk

Cited by 16 publications

References 75 publications

Rapid ring‐opening polymerization of 1,4‐dioxan‐2‐one initiated by titanium alkoxides

Rapid ring‐opening polymerization of 1,4‐dioxan‐2‐one initiated by titanium alkoxides

Synthesis of metal‐free poly(p‐dioxanone) by phosphazene base catalyzed ring‐opening polymerization

The influence of coexisted monomer on thermal, mechanical, and hydrolytic properties of poly(p‐dioxanone)

Contact Info

Product

Resources

About