Macromolecular engineering viaring-opening polymerization (2): l-lactide/trimethylene carbonate copolymerization – kinetic and microstructural control via catalytic tuning

Literature Information

Publication Date 2013-04-19
DOI 10.1039/C3PY00397C
Impact Factor 5.582
Authors

William Guerin, Martine Slawinski, Jean-Michel Brusson, Sophie M. Guillaume, Jean-François Carpentier


View Original

Abstract

Copolymerization of L-LA and TMC has been achieved with binary systems, associating either a metal-based (pre)catalyst or an organocatalyst with benzyl alcohol (BnOH) acting as a co-initiator and a chain transfer agent. Kinetic monitoring indicated that copolymerizations mediated by the zinc-β-diketiminate system [(BDI)Zn{N(SiMe3)2}]/BnOH proceed by preferential consumption of L-LA first and then of TMC, in contrast to homopolymerizations of the individual monomers that progress roughly at the same rate. In striking contrast, systems based on metal triflates, M(OTf)3/BnOH (M = Al, Bi, Yb), copolymerize TMC faster than L-LA, as established for the first time, while these systems also homopolymerize the individual monomers at about the same rate. Eventually, the [(BDI)Zn{N(SiMe3)2}]/BnOH and M(OTf)3/BnOH systems produce P(LLA-grad-TMC) gradient copolymers featuring PLLA and PTMC blocks of significant length (ca. 10 units with Al-, Yb-; ca. 6 units with Zn-, Bi-based systems), as confirmed by 13C NMR analyses. On the other hand, copolymerizations mediated by the guanidine-based organocatalyst system TBD/BnOH (TBD = 1,5,7-triazabicyclo[4.4.0]dec-5-ene) gave P(LLA-ran-TMC) random copolymers. Optimal control of molar masses and dispersities, along with minimized transesterifications, is achieved with the zinc and ytterbium systems. While metal triflates induce partial decarboxylation of TMC units, the zinc and TBD systems are perfectly chemoselective. Kinetic and microstructural control in random copolymerization of L-LA and TMC can thus be achieved via catalytic tuning.

Related Literature

Supported ATRP of fluorinated methacrylates in supercritical carbon dioxide: preparation of scCO2 soluble polymers with low catalytic residues

Bruno Grignard, Cédric Calberg, Christine Jérôme, Wenxin Wang, Steven Howdle, Christophe Detrembleur

2008-10-01 Communication

DOI: 10.1039/B812297K

Silver-enhanced fluorescence emission of single quantum dot nanocomposites

Yi Fu, Jian Zhang, Joseph R. Lakowicz

2008-11-19 Communication

DOI: 10.1039/B816736B

Remarkable switching behavior of bimodally stimuli-responsive photochromic dithienylethenes with redox-active organometallic attachments

Keiko Motoyama, Takashi Koike, Munetaka Akita

2008-10-02 Communication

DOI: 10.1039/B809318K

Enzyme-mediated sol–gel processing of alkoxysilanes

Mark Frampton, Ateeya Vawda, Jackie Fletcher, Paul M. Zelisko

2008-09-23 Communication

DOI: 10.1039/B812389F

An unprecedented lanthanide phosphinidene halide: synthesis, structure and reactivity

Peng Cui, Yaofeng Chen, Xin Xu, Jie Sun

2008-09-24 Communication

DOI: 10.1039/B813075B

Epoxy functionalised poly(ε-caprolactone): synthesis and application

Jiaxiang Zhou, Wenxin Wang, Silvia Villarroya, Kristofer J. Thurecht, Steven M. Howdle

2008-10-01 Communication

DOI: 10.1039/B810297J

Facile synthesis of continuous Pt island networks and their electrochemical properties for methanol electrooxidation

Jitendra N. Tiwari, Fu-Ming Pan, Rajanish N . Tiwari, S.K . Nandi

2008-11-06 Communication

DOI: 10.1039/B813935K

Sn(iv) phosphonates as catalysts in solvent-free Baeyer–Villiger oxidations using H2O2

Sharath Kirumakki, Sandani Samarajeewa, Robert Harwell, Atashi Mukherjee, Rolfe H. Herber, Abraham Clearfield

2008-10-08 Communication

DOI: 10.1039/B807938B

A robust strategy for the preparation of libraries of metallopeptides. A new paradigm for the discovery of targeted molecular imaging and therapy agents

Andrea F. Armstrong, Nick Oakley, Shannon Parker, Patrick W. Causey, Jennifer Lemon, Alfredo Capretta, Craig Zimmerman, John Joyal, Francis Appoh, Jon Zubieta, John W. Babich, Gurmit Singh, John F. Valliant

2008-09-24 Communication

DOI: 10.1039/B810706H

You might also like

Compound Q&A

What is Ethyl 3-cyclohexylpropanoate (CAS: 10094-36-7)?

Ethyl 3-cyclohexylpropanoate is a clear, colorless to light yellow liquid with a...

10094-36-7Ethyl 3-cyclohexylpr...
Compound Q&A

How should waste containing 2-(Hydroxymethyl)-5-(methoxycarbonyl)-6-methyl-4-(2-nitrophenyl)nicotinic acid (CAS: 34783-31-8) be handled?

Waste containing 2-(Hydroxymethyl)-5-(methoxycarbonyl)-6-methyl-4-(2-nitrophenyl...

34783-31-82-(Hydroxymethyl)-5-...
Compound Q&A

How should waste containing 2,4,6-Tris(pentafluoroethyl)-1,3,5-triazine (CAS: 858-46-8) be handled?

Waste containing 2,4,6-Tris(pentafluoroethyl)-1,3,5-triazine (CAS: 858-46-8) sho...

858-46-82,4,6-Tris(pentafluo...
Compound Q&A

What precautions should be taken when handling Chloroac-nle-oh (CAS: 56787-36-1)?

When handling Chloroac-nle-oh (CAS: 56787-36-1), it is essential to wear appropr...

56787-36-1Chloroac-nle-oh
Compound Q&A

What industries use Ethyl 6-phenylimidazo[2,1-b][1,3]thiazole-3-carboxylate (CAS: 752244-05-6)?

Ethyl 6-phenylimidazo[2,1-b][1,3]thiazole-3-carboxylate is primarily used in the...

752244-05-6Ethyl 6-phenylimidaz...
Compound Q&A

Are there alternatives to alpha-(2-Bromophenyl)benzylamine (CAS: 55095-15-3) in synthesis?

Alternatives to alpha-(2-Bromophenyl)benzylamine (CAS: 55095-15-3) in synthesis ...

55095-15-3alpha-(2-Bromophenyl...
Compound Q&A

How should waste containing 2-Chloro-5-methoxypyridine (CAS: 139585-48-1) be handled?

Waste containing 2-Chloro-5-methoxypyridine (CAS: 139585-48-1) should be managed...

139585-48-12-Chloro-5-methoxypy...
Compound Q&A

What industries use 1-(4-Methoxyphenyl)-2,5-dimethyl-1H-pyrrole (CAS: 5044-27-9)?

1-(4-Methoxyphenyl)-2,5-dimethyl-1H-pyrrole (CAS: 5044-27-9) is used in various ...

5044-27-91-(4-Methoxyphenyl)-...
Compound Q&A

Are there alternatives to 3-Bromo-5-(N-Boc)aminomethylisoxazole (CAS: 903131-45-3) in synthesis?

There are alternative reagents and compounds that can be used in the synthesis o...

903131-45-33-Bromo-5-(N-Boc)ami...
Compound Q&A

What is Tungsten(IV) oxide (CAS: 12036-22-5)?

Tungsten(IV) oxide, also known as tungsten dioxide, is a chemical compound with ...

12036-22-5Tungsten(IV) oxide

Source Journal

Polymer Chemistry

Polymer Chemistry
CiteScore: 8.6
Self-citation Rate: 7.3%
Articles per Year: 457

Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.

Recommended Compounds

Recommended Suppliers

Disclaimer
This page provides academic journal information for reference and research purposes only. We are not affiliated with any journal publishers and do not handle publication submissions. For publication-related inquiries, please contact the respective journal publishers directly.
If you notice any inaccuracies in the information displayed, please contact us at support@chemtradehub.com. We will promptly review and address your concerns.