Copolymerization of cyclic esters, epoxides and anhydrides: evidence of the dual role of the monomers in the reaction mixture

Isnard, Florence; Carratù, Mario; Lamberti, Marina; Venditto, Vincenzo; Mazzeo, Mina

doi:10.1039/c8cy01174e

Cited by 43 publications

(34 citation statements)

References 71 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently we showed that Cr(III) or Al(III) catalyst systems follow the same mechanism and yielded block polyesters 23,28 . Other researchers have successfully applied the same switchable polymerization method to di-zinc 20 , di-aluminium 29 and transition metal 30 catalysts. A requirement for successful catalysis is that the ROCOP cycles yield highly alternating polyesters, i.e.…”

Section: Introductionmentioning

confidence: 99%

Easy access to oxygenated block polymers via switchable catalysis

et al. 2019

View full text Add to dashboard Cite

Oxygenated block polyols are versatile, potentially bio-based and/or degradable materials widely applied in the manufacture of coatings, resins, polyurethanes and other products. Typical preparations involve multistep syntheses and/or macroinitiator approaches. Here, a straightforward and well-controlled one-pot synthesis of ABA triblocks, namely poly(ether- b -ester- b -ether), and ABCBA pentablocks, of the form poly(ester- b -ether- b -ester’- b -ether- b -ester), using a commercial chromium catalyst system is described. The polymerization catalysis exploits mechanistic switches between anhydride/epoxide ring-opening copolymerization, epoxide ring-opening polymerization and lactone ring-opening polymerization without requiring any external stimuli. Testing a range of anhydrides, epoxides and chain-transfer agents reveals some of the requirements and guidelines for successful catalysis. Following these rules of switch catalysis with multiple monomer additions allows the preparation of multiblock polymers of the form (ABA) n up to 15 blocks. Overall, this switchable catalysis delivers polyols in a straightforward and highly controlled manner. As proof of potential for the materials, methods to post-functionalize and/or couple the polyols to make higher polymers are demonstrated.

show abstract

Section: Introductionmentioning

confidence: 99%

Easy access to oxygenated block polymers via switchable catalysis

et al. 2019

View full text Add to dashboard Cite

show abstract

“…One common strategy for tuning the polymer properties such as glass transition temperature ( T g ) is to incorporate additional monomers to form block or random copolymers [ 51 , 52 , 53 , 54 ]. Given the versatility of the current zinc catalysts for various epoxides and anhydrides, we were interested to see if terpolymerization could be achieved and how it could affect the properties of the resulting terpolymers.…”

Section: Resultsmentioning

confidence: 99%

Zinc Amido-Oxazolinate Catalyzed Ring Opening Copolymerization and Terpolymerization of Maleic Anhydride and Epoxides

et al. 2020

View full text Add to dashboard Cite

Ring opening copolymerization (ROCOP) of epoxides and cyclic anhydrides has become an attractive approach for the synthesis of biodegradable polyesters with various compositions. Encouraged by the efficiency and versatility of a series of amido-oxazolinate zinc complexes, in this study they were shown to be active catalysts for the synthesis of unsaturated polyesters via ROCOP of maleic anhydride and various epoxides. The relative activity of epoxides in these reactions was observed to be styrene oxide > cyclohexene oxide > phenyl glycidyl ether, which could be correlated with the electronic and steric features of the substrate. To provide more structural possibilities for the polyesters, the difference in epoxide reactivity was exploited in an attempt to prepare block terpolymers from one anhydride and two epoxides. Terpolymerization was carried out in one or two steps in a single pot. The thermal characterization by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques suggested that the resulting materials were mostly random terpolymers.

show abstract

“…The highest performances of the latter were attributed to possible cooperative effects between the two metal centers in close proximity due to the shorter backbone. The complex also proved as an efficient catalyst for the homo-and copolymerization of other cyclic esters (L-LA, ε-CL and β-BL), epoxides and anhydrides [133].…”

Section: Aluminummentioning

confidence: 99%

Synthesis of Biodegradable Polymers: A Review on the Use of Schiff-Base Metal Complexes as Catalysts for the Ring Opening Polymerization (ROP) of Cyclic Esters

2020

View full text Add to dashboard Cite

show abstract

Copolymerization of cyclic esters, epoxides and anhydrides: evidence of the dual role of the monomers in the reaction mixture

Abstract: A block copolyester derived from ROCOP of CHO/SA followed by ROP of ε-CL was obtained from the mixture of monomers. The lactone comonomer acts as an endogen cocatalyst during the SA/CHO ROCOP step and as a monomer during ROP.

Cited by 43 publications

References 71 publications

Easy access to oxygenated block polymers via switchable catalysis

Easy access to oxygenated block polymers via switchable catalysis

Zinc Amido-Oxazolinate Catalyzed Ring Opening Copolymerization and Terpolymerization of Maleic Anhydride and Epoxides

Synthesis of Biodegradable Polymers: A Review on the Use of Schiff-Base Metal Complexes as Catalysts for the Ring Opening Polymerization (ROP) of Cyclic Esters

Contact Info

Product

Resources

About