Ring-opening polymerization of ω-6-hexadecenlactone by a salicylaldiminato aluminum complex: a route to semicrystalline and functional poly(ester)s

Fuoco, Tiziana; Meduri, Angelo; Lamberti, Marina; Venditto, Vincenzo; Pellecchia, Claudio; Pappalardo, Daniela

doi:10.1039/c4py01445f

Cited by 34 publications

(59 citation statements)

References 78 publications

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“…9−11 Copolymerization of macrolactones and small-ring (strained) lactones has been reported by several authors. 9−14 Even though control in these types of polymerization is generally difficult due to the low ring strain of the macrolactone and the associated entropic nature of the polymerization, 15 stable block copolymer architectures could be synthesized using a sequential feed polymerization approach, 14,16 or even by a single-feed polymerization.…”

Section: ■ Introductionmentioning

confidence: 99%

Block Copolymers of “PE-Like” Poly(pentadecalactone) and Poly(l-lactide): Synthesis, Properties, and Compatibilization of Polyethylene/Poly(l-lactide) Blends

et al. 2015

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Block copolymers consisting of a polyethylene block and a polar polymer block are interesting structures for the compatibilization of polyethylene/polar polymer blends or polyethylene-based composites. Since the synthesis of polyethylene-based block copolymers is an elaborate process, diblock copolymers consisting of “polyethylene-like” poly(pentadecalactone) (PPDL) and poly(l-lactide) (PLLA) were synthesized using a one-pot, sequential-feed ring-opening polymerization of pentadecalactone (PDL) and l-lactide (LLA). The peculiar activity of the used aluminum salen catalysts yielded a block copolymer consisting of two blocks with both a high dispersity, as a result of intrablock transesterification. Interestingly, interblock transesterification was effectively suppressed. The obtained poly(PDL-block-LLA) of various block lengths showed coincidental crystallization of the two blocks with an associated microphase-separated morphology, in which PLLA spheres with a high dispersity are distributed within the PPDL matrix. The complex morphologies is believed to arise from the presence of a whole range of block sizes as a consequence of the large dispersity of both blocks. The application of these block copolymers as compatibilizers for high density polyethylene (HDPE)/PLLA blends led to a clear change in blend morphology and a steep decrease in particle size of the dispersed phase. Furthermore, addition of the block copolymers to blends of linear low density polyethylene (LLDPE) and PLLA led to a significant increase in adhesion between the two phases. For both HDPE/PLLA and LLDPE/PLLA blends, the compatibilization efficiency of the poly(PDL-block-LLA) increased when the length of the PPDL block was increased. The presented results clearly show that PPDL can function as a substituent for various types of polyethylene, which opens up a new method for compatibilizing polyethylene with polar polymers using easy attainable “PE-like” block copolymers.

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Section: ■ Introductionmentioning

confidence: 99%

Block Copolymers of “PE-Like” Poly(pentadecalactone) and Poly(l-lactide): Synthesis, Properties, and Compatibilization of Polyethylene/Poly(l-lactide) Blends

et al. 2015

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“…controlled polymerization with absence of transesterification reaction, and a certain living behavior [36]. This interesting result prompted us to explore the reactivity of the same catalytic system also in the ROP not only of other conventional cyclic esters, i.e., glycolide [37], but also of large ring macrolactone [38] and of novel synthetized thiol-functionalized lactide [39]. A large variety of aluminum-based salicylaldiminato complexes have been described and used in the ROP of various cyclic esters, their structural features are summarized in Table 1 with reference to the proper literature.…”

Section: Dimethyl(salicilaldiminato)aluminum Complexesmentioning

confidence: 99%

“…A large variety of aluminum-based salicylaldiminato complexes have been described and used in the ROP of various cyclic esters, their structural features are summarized in Table 1 with reference to the proper literature. macrolactone [38] and of novel synthetized thiol-functionalized lactide [39]. A large variety of aluminum-based salicylaldiminato complexes have been described and used in the ROP of various cyclic esters, their structural features are summarized in Table 1 with reference to the proper literature.…”

Section: Dimethyl(salicilaldiminato)aluminum Complexesmentioning

confidence: 99%

“…This interesting result prompted us to explore the reactivity of the same catalytic system also in the ROP not only of other conventional cyclic esters, i.e., glycolide [37], but also of large ring macrolactone [38] and of novel synthetized thiol-functionalized lactide [39].…”

Section: Dimethyl(salicilaldiminato)aluminum Complexesmentioning

confidence: 99%

“…Interestingly, the dimethyl(salicylaldiminato) aluminum compound 3 resulted in active catalysts for the ROP of 6HDL to high molecular weight polymer, P6HDL, in a controlled fashion (Scheme 7). Such a monomer could represent a useful platform for the synthesis of semicrystalline and functional polyethylene-like polyesters [38].…”

Section: Ring-opening Polymerization Of Macrolactonesmentioning

confidence: 99%

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Aluminum Alkyl Complexes Bearing Salicylaldiminato Ligands: Versatile Initiators in the Ring-Opening Polymerization of Cyclic Esters

Fuoco

Pappalardo

2017

Catalysts

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Linear aliphatic polyesters are degradable thermoplastic polymers, which can be obtained by ring-opening polymerization (ROP) of cyclic esters through a coordination-insertion mechanism. Aluminum based organometallic complexes have a leading position as efficient catalysts for this polymerization process. Aluminumalkyl complexes bearing salicylaldiminato ligands, although less explored, have been shown to be efficient and versatile catalysts for the ROP of various cyclic esters. These species have the potential to function as active catalysts in the ROP because of their less coordinatively saturated nature with respect to analogous SALEN-type complexes. They have been used as efficient catalysts in the ROP of commercially available cyclic esters, such as ε-caprolactone, L-lactide, rac-lactide, and glycolide. Moreover, they resulted in efficient catalysts for the ROP of cyclic esters with large ring-size and for the ROP of functionalized lactide. Furthermore, they have been used in the co-and ter-polymerization of various cyclic esters affording well controlled polymerization and a plethora of microstructural architectures, ranging from random to block to multiblock.

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Copolymerization and terpolymerization of glycolide with lactones by dimethyl(salicylaldiminato)aluminum compounds

Fuoco

Meduri

Lamberti

et al. 2015

J of Applied Polymer Sci

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The aliphatic poly(esters) are the most common biodegradable and biocompatible synthetic materials used by far for diverse biomedical applications. Co-polymers and ter-polymers of glycolide with e-caprolactone and lactide are produced in the presence of dimethyl aluminum compounds, bearing salicylaldiminato bidentate ligands differing for the steric hindrance on the ortho position of the phenolato ring. The formation of random poly[glycolide-co-(e-caprolactone)] samples is favored with more encumbered catalyst. Transesterification reactions of the second mode also contribute to randomize the structure. Copolymers from semicrystalline to amorphous are produced by decreasing the glycolide/e-caprolactone feed ratio. The terpolymerization of glycolide with e-caprolactone and rac-lactide with the same catalysts affords amorphous and random poly[(glycolide-co-lactide-co-(e-caprolactone)] samples. The incorporation of the monomers is in this case determined by the bulkiness of the catalysts and by the higher coordination ability of the cyclic diesters.

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Ring-opening polymerization of ω-6-hexadecenlactone by a salicylaldiminato aluminum complex: a route to semicrystalline and functional poly(ester)s

Abstract: The homo and co-polymerization of a large ring size lactone afforded unsaturated poly(esters), further modified to functional thermoplastic materials.

Cited by 34 publications

References 78 publications

Block Copolymers of “PE-Like” Poly(pentadecalactone) and Poly(l-lactide): Synthesis, Properties, and Compatibilization of Polyethylene/Poly(l-lactide) Blends

Block Copolymers of “PE-Like” Poly(pentadecalactone) and Poly(l-lactide): Synthesis, Properties, and Compatibilization of Polyethylene/Poly(l-lactide) Blends

Aluminum Alkyl Complexes Bearing Salicylaldiminato Ligands: Versatile Initiators in the Ring-Opening Polymerization of Cyclic Esters

Copolymerization and terpolymerization of glycolide with lactones by dimethyl(salicylaldiminato)aluminum compounds

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