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Title: Crystalline aliphatic polyesters from eight‐membered cyclic (di)esters
Abstract

Ring‐opening polymerization (ROP) of lactones or cyclic (di)esters is a powerful method to produce well‐defined, high‐molecular‐weight (bio)degradable aliphatic polyesters. While the ROP of lactones of various ring sizes has been extensively studied, the ROP of the simplest eight‐membered lactone, 7‐heptanolactone (7‐HL), has not been reported using metal‐based catalysts. Accordingly, this contribution reports the ROP of 7‐HL via metal‐catalyzed coordinative‐insertion polymerization to the corresponding high‐molecular‐weight polyester, poly(7‐hydroxyheptanoate) (P7HHp). The resulting P7HHp is a semi‐crystalline material, with aTmof 68 °C, which is ~10 °C higher than poly(ε‐caprolactone) derived from the seven‐membered lactone. Mechanical testing showed that P7HHp is a hard and tough plastic, with elongation at break >670%. P7HHp‐based polyesters with higherTmvalues have been achieved through stereoselective copolymerization of 7‐HL with an eight‐membered cyclic diester, racemic dimethyl diolide (rac‐8DLMe), known to lead to highTmpoly(3‐hydroxyburtyrate) (P3HB). Notably, catalyst's strong kinetic preference for polymerizingrac‐8DLMeover 7‐HL in the 1/1 comonomer mixture rendered the formation of di‐block copolymer P3HB‐b‐P7HHp, showing two crystalline domains withTm1 ~ 65 °C andTm2 ~ 160 °C. Semi‐crystalline random copolymers withTmup to 164 °C have also been obtained by adjusting copolymerization conditions. Mechanical testing showed that P3HB‐b‐P7HHp can synergistically combine the high modulus of isotactic P3HB with the high ductility of P7HHp.

 
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Award ID(s):
1955482
NSF-PAR ID:
10385803
Author(s) / Creator(s):
 ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Journal of Polymer Science
Volume:
60
Issue:
24
ISSN:
2642-4150
Page Range / eLocation ID:
p. 3478-3488
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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