A novel tin-based imidazolium-modified montmorillonite catalyst for the preparation of poly(butylene terephthalate)-based nanocomposites using in situ entropically-driven ring-opening polymerization

A novel alkylimidazolium salt incorporating a 2,2-di-n-butyl[1,3,2]dioxastannolane moiety was synthesized and characterized. Its effectiveness as a transesterification catalyst in the entropically-driven ring-opening polymerization (ED-ROP) of macrocyclic oligomers of butylene terephthalate (BT-MCOs) was comparable to that of other tin-based transesterification catalysts. A supported version of the catalyst was prepared by ion exchange with the sodium cations present in montmorillonite. X-Ray analysis indicated the imidazolium species entered the galleries between the silicate layers. The supported catalyst was significantly more thermally stable than the non-supported catalyst. Poly(butylene terephthalate)–clay nanocomposites were obtained by the in situ ED-ROP of BT-MCOs intercalated between the clay layers, catalyzed by either the supported tin-based catalyst or by a catalyst prepared in situ from a supported imidazolium salt with diol moieties and di-n-butyldimethoxytin. X-Ray diffraction and transmission electron microscopy indicated that the ensuing nanocomposites exhibit a mix of intercalated and exfoliated silicate nanolayers.

[1]  P. Hodge Cyclodepolymerization as a method for the synthesis of macrocyclic oligomers , 2014 .

[2]  P. Hodge Entropically driven ring-opening polymerization of strainless organic macrocycles. , 2014, Chemical reviews.

[3]  S. Hong,et al.  Temperature-dependent decyclopolymerization of cyclic oligomers and the implication on destructuring layered nanosheets for nanocomposite reinforcement , 2013 .

[4]  Wei Yu,et al.  Effect of thermally reduced graphite oxide (TrGO) on the polymerization kinetics of poly(butylene terephthalate) (pCBT)/TrGO nanocomposites prepared by in situ ring-opening polymerization of cyclic butylene terephthalate , 2013 .

[5]  J. Ganster,et al.  Nanocomposites based on aromatic polyesters and organically modified clay , 2013 .

[6]  J. Karger‐Kocsis,et al.  Preparation and characterization of in situ polymerized cyclic butylene terephthalate/graphene nanocomposites , 2013, Journal of Materials Science.

[7]  P. Kubisa,et al.  Microspheres from stereocomplexes of polylactides containing ionic liquid end-groups , 2012 .

[8]  V. Mittal Modification of montmorillonites with thermally stable phosphonium cations and comparison with alkylammonium montmorillonites , 2012 .

[9]  U. Yilmazer,et al.  Novel thermally stable organo-montmorillonites from phosphonium and imidazolium surfactants , 2011 .

[10]  X. Zhu,et al.  Recent advances in entropy-driven ring-opening polymerizations , 2011 .

[11]  P. Stagnaro,et al.  Syntheses of random PET‐co‐PTTs and some related copolyesters by entropically‐driven ring‐opening polymerizations and by melt blending: Thermal properties and crystallinity , 2011 .

[12]  P. Stagnaro,et al.  A Possible Means to Assist the Processing of PET, PTT and PBT , 2010 .

[13]  M. Colonna,et al.  Improved dispersion of clay platelets in poly(butylene terephthalate) nanocomposite by ring‐opening polymerization of cyclic oligomers: Effect of the processing conditions and comparison with nanocomposites obtained by melt intercalation , 2009 .

[14]  Fu-Yuan Wu,et al.  Poly(butylene terephthalate)/organoclay nanocomposites prepared by in-situ bulk polymerization with cyclic poly(butylene terephthalate) , 2009 .

[15]  P. Stagnaro,et al.  High throughput synthesis of polyesters using entropically driven ring-opening polymerizations. , 2008, Journal of combinatorial chemistry.

[16]  P. Lafleur,et al.  Thermal decomposition of various alkyl onium organoclays: Effect on polyethylene terephthalate nanocomposites' properties , 2008 .

[17]  D. Brunelle Cyclic oligomer chemistry , 2008 .

[18]  B. R. Nayak,et al.  Highly Exfoliated Poly(ε-caprolactone)/organomontmorillonite Nanocomposites Prepared by In Situ Polymerization , 2008 .

[19]  Paul H. Maupin,et al.  Synthesis of imidazolium salts and their application in epoxy montmorillonite nanocomposites , 2006 .

[20]  T. Tsai,et al.  Preparation of Exfoliated Polyester/Clay Nanocomposites , 2005 .

[21]  H. Kricheldorf Biodegradable polymers with variable architectures via ring‐expansion polymerization , 2004 .

[22]  J. Gilman,et al.  Thermal degradation studies of alkyl-imidazolium salts and their application in nanocomposites , 2004 .

[23]  H. C. Aspinall,et al.  Modular chiral polyether podands and their lanthanide complexes , 2003 .

[24]  C. Ou Crystallization behavior and thermal stability of poly(trimethylene terephthalate)/clay nanocomposites , 2003 .

[25]  Suprakas Sinha Ray,et al.  POLYMER/LAYERED SILICATE NANOCOMPOSITES: A REVIEW FROM PREPARATION TO PROCESSING , 2003 .

[26]  S. Kukureka,et al.  Poly(butylene terephthalate) nanocomposites prepared by in-situ polymerization , 2003 .

[27]  L. Mathias,et al.  Effects of melt-processing conditions on the quality of poly(ethylene terephthalate) montmorillonite clay nanocomposites† , 2002 .

[28]  S. Nishimura,et al.  High-Modulus Poly(ethylene terephthalate)/Expandable Fluorine Mica Nanocomposites with a Novel Reactive Compatibilizer , 2002 .

[29]  Wei Xie,et al.  Thermal Degradation Chemistry of Alkyl Quaternary Ammonium Montmorillonite , 2001 .

[30]  P. Dubois,et al.  Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials , 2000 .

[31]  H. Kricheldorf,et al.  Macrocycles, 1. Macrocyclic polymerizations of (thio)lactones – stepwise ring expansion and ring contraction , 1998 .

[32]  S. Scapecchi,et al.  Group 14 organometallic reagents. 9. Organotin-mediated monoacylation of diols with reversed chemoselectivity: a convenient synthetic method , 1990 .

[33]  R. E. Smallman,et al.  An assessment of high voltage electron microscopy (HVEM). An invited review , 1977 .