Journal ArticleDOI
Guanidine and Amidine Organocatalysts for Ring-Opening Polymerization of Cyclic Esters
Bas G. G. Lohmeijer,Russell C. Pratt,Frank A. Leibfarth,John W. Logan,David A. Long,Andrew P. Dove,Fredrik Nederberg,Jeongsoo Choi,Charles G. Wade,Robert M. Waymouth,James L. Hedrick +10 more
TLDR
In this article, the ring-opening polymerization (ROP) of cyclic esters such as lactide (LA), δ-valerolactone (VL), and e-caprolactone(CL) was achieved.Abstract:
1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), N-methyl-TBD (MTBD), and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are effective organocatalysts for the ring-opening polymerization (ROP) of cyclic esters such as lactide (LA), δ-valerolactone (VL), and e-caprolactone (CL). TBD is shown to polymerize LA, VL, and CL in a fast and controlled manner, whereas MTBD and DBU polymerized LA and addition of a thiourea cocatalyst led to the ROP of VL and CL being achieved. Each of the catalysts produced polymers displaying high end group fidelity, good correlation between theoretical and observed molecular weight, and linear relationships between conversion and molecular weight. The enhanced activity of TBD relative to MTBD and DBU is attributed to its bifunctionality, enabling the simultaneous activation of both the cyclic ester monomer and the alcohol group of the initiator/propagating species. Temperature-dependent NMR studies generated individual association constants for MTBD with benzyl alcohol and thiourea with VL. ...read more
Citations
More filters
Journal ArticleDOI
Benzyl bispidine as an efficient replacement for (−)-sparteine in ring opening polymerisation
TL;DR: In this article, the synthesis and application of a dibenzyl-functionalized bispidine, in combination with 1-(3,5-bis(trifluoromethyl)phenyl)-3-cyclohexylthiourea (TU) co-catalyst, has been demonstrated to be an excellent catalyst for the controlled ring-opening polymerisation (ROP) of lactide and cyclic carbonate monomers.
Journal ArticleDOI
An efficient avenue to poly(styrene)‐block‐poly(ε‐caprolactone) polymers via switching from RAFT to hydroxyl functionality: Synthesis and characterization
TL;DR: In this article, the ring-opening polymerization (ROP) of e-caprolactone (e-CL) was conducted under organocatalysis employing 1,5,7-triazabicyclo[4.0]dec-5-ene (TBD).
Journal ArticleDOI
Synthesis of block and end-functionalized polyesters by triflimide-catalyzed ring-opening polymerization of ε-caprolactone, 1,5-dioxepan-2-one, and rac-lactide
TL;DR: In this paper, a ring-opening polymerization (ROP) of cyclic esters, such as e-caprolactone, 1,5-dioxepan-2-one, and racemic lactide using the combination of 3-phenyl-1-propanol as the initiator and triflimide (HNTf2) as the catalyst at room temperature with the [monomer]0/[initiator]0 ratio of 50/1 was investigated.
Journal ArticleDOI
Cyclopropenimine Superbases: Competitive Initiation Processes in Lactide Polymerization.
Tyler S. Stukenbroeker,Jeffrey S. Bandar,Xiangyi Zhang,Tristan H. Lambert,Robert M. Waymouth +4 more
TL;DR: Model studies and comparative experiments with guanidine and phosphazene catalysts revealed the subtle influence of the nature of the superbase on competitive initiation processes.
Journal ArticleDOI
Polyester Stereocomplexes Beyond PLA: Could Synthetic Opportunities Revolutionize Established Material Blending?
TL;DR: This review summarizes the current literature regarding stereocomplexation of different polyesters based on α- as well as β-hydroxy acids beyond the well-known poly(lactic acid) and synthetic approaches needed to obtain and analyze isotactic polyesters are summarized.
References
More filters
Journal ArticleDOI
Controlled ring-opening polymerization of lactide and glycolide.
TL;DR: This work focuses on the characterization of the phytochemical components of Lactide ROP and their role in the regulation of cell reprograming.
Journal ArticleDOI
Polymerization of Lactide with Zinc and Magnesium β-Diiminate Complexes: Stereocontrol and Mechanism
Bradley M. Chamberlain,Ming Cheng,David Roger Moore,Tina M. Ovitt,Emil B. Lobkovsky,Geoffrey W. Coates +5 more
TL;DR: The substituents on the beta-diiminate ligand exert a significant influence upon the course of the polymerizations, affecting both the degree of stereoselectivity and the rate of polymerization.
Journal ArticleDOI
A review of biodegradable polymers: uses, current developments in the synthesis and characterization of biodegradable polyesters, blends of biodegradable polymers and recent advances in biodegradation studies
TL;DR: A review of the uses of biodegradable polymers in terms of their relevance within current plastic waste management of packaging materials, biomedical applications and other uses is presented in this paper.
Journal ArticleDOI
Extension of the self-consistent spectrophotometric basicity scale in acetonitrile to a full span of 28 pKa units: unification of different basicity scales.
Ivari Kaljurand,Agnes Kütt,Lilli Sooväli,Toomas Rodima,Vahur Mäemets,and Ivo Leito,Ilmar A. Koppel +6 more
TL;DR: The earlier compiled self-consistent spectrophotometric basicity scale in acetonitrile (AN) was expanded to range from 3.8 to 32.0 pK(a) units, that is 28 orders of magnitude, and 54 new relative basicity measurements were carried out and 37 new compounds were introduced to the scale.
Journal ArticleDOI
Stereochemistry of Lactide Polymerization with Chiral Catalysts: New Opportunities for Stereocontrol Using Polymer Exchange Mechanisms
Tina M. Ovitt,Geoffrey W. Coates +1 more
TL;DR: A polymer exchange mechanism is proposed to account for the PLA microstructures resulting from rac-4, which polymerizes meso-lactide to syndiotactic poly(lactic acid) (PLA) and heterotactic and isotactic stereoblock PLA, respectively.