PMID- 29543743
OWN - NLM
STAT- MEDLINE
DCOM- 20180828
LR  - 20230926
IS  - 1420-3049 (Electronic)
IS  - 1420-3049 (Linking)
VI  - 23
IP  - 3
DP  - 2018 Mar 15
TI  - Silyl Ketene Acetals/B(C(6)F(5))(3) Lewis Pair-Catalyzed Living Group Transfer 
      Polymerization of Renewable Cyclic Acrylic Monomers.
LID - 10.3390/molecules23030665 [doi]
LID - 665
AB  - This work reveals the silyl ketene acetal (SKA)/B(C(6)F(5))(3) Lewis pair-catalyzed 
      room-temperature group transfer polymerization (GTP) of polar acrylic monomers, 
      including methyl linear methacrylate (MMA), and the biorenewable cyclic monomers 
      gamma-methyl-alpha-methylene-gamma-butyrolactone (MMBL) and alpha-methylene-gamma-butyrolactone (MBL) 
      as well. The in situ NMR monitored reaction of SKA with B(C(6)F(5))(3) indicated the 
      formation of Frustrated Lewis Pairs (FLPs), although it is sluggish for MMA 
      polymerization, such a FLP system exhibits highly activity and living GTP of MMBL 
      and MBL. Detailed investigations, including the characterization of key reaction 
      intermediates, polymerization kinetics and polymer structures have led to a 
      polymerization mechanism, in which the polymerization is initiated with an 
      intermolecular Michael addition of the ester enolate group of SKA to the vinyl 
      group of B(C(6)F(5))(3)-activated monomer, while the silyl group is transferred to the 
      carbonyl group of the B(C(6)F(5))(3)-activated monomer to generate the 
      single-monomer-addition species or the active propagating species; the 
      coordinated B(C(6)F(5))(3) is released to the incoming monomer, followed by repeated 
      intermolecular Michael additions in the subsequent propagation cycle. Such 
      neutral SKA analogues are the real active species for the polymerization and are 
      retained in the whole process as confirmed by experimental data and the chain-end 
      analysis by matrix-assisted laser desorption/ionization time of flight mass 
      spectroscopy (MALDI-TOF MS). Moreover, using this method, we have successfully 
      synthesized well-defined PMMBL-b-PMBL, PMMBL-b-PMBL-b-PMMBL and random copolymers 
      with the predicated molecular weights (M(n)) and narrow molecular weight 
      distribution (MWD).
FAU - Hu, Lu
AU  - Hu L
AD  - State Key Laboratory of Supramolecular Structure and Materials, College of 
      Chemistry, Jilin University, Changchun 130012, China. hulu14@mails.jlu.edu.cn.
FAU - Zhao, Wuchao
AU  - Zhao W
AD  - State Key Laboratory of Supramolecular Structure and Materials, College of 
      Chemistry, Jilin University, Changchun 130012, China. zhaowc16@mails.jlu.edu.cn.
FAU - He, Jianghua
AU  - He J
AD  - State Key Laboratory of Supramolecular Structure and Materials, College of 
      Chemistry, Jilin University, Changchun 130012, China. hjh2015@jlu.edu.cn.
FAU - Zhang, Yuetao
AU  - Zhang Y
AUID- ORCID: 0000-0002-6406-1959
AD  - State Key Laboratory of Supramolecular Structure and Materials, College of 
      Chemistry, Jilin University, Changchun 130012, China. ytzhang2009@jlu.edu.cn.
LA  - eng
PT  - Journal Article
DEP - 20180315
PL  - Switzerland
TA  - Molecules
JT  - Molecules (Basel, Switzerland)
JID - 100964009
RN  - 0 (Acetals)
RN  - 0 (Ketones)
RN  - 196OC77688 (Methylmethacrylate)
RN  - 362Y256BOL (alpha-methylene gamma-butyrolactone)
RN  - OL659KIY4X (4-Butyrolactone)
SB  - IM
MH  - 4-Butyrolactone/*analogs & derivatives/chemistry
MH  - Acetals/*chemistry
MH  - Catalysis
MH  - Ketones/chemistry
MH  - Methylmethacrylate/*chemistry
MH  - Molecular Structure
MH  - Polymerization
PMC - PMC6017534
OTO - NOTNLM
OT  - B(C6F5)3
OT  - Frustrated Lewis Pair
OT  - group transfer polymerization
OT  - silyl ketene acetal
COIS- The authors declare no conflict of interest.
EDAT- 2018/03/16 06:00
MHDA- 2018/08/29 06:00
PMCR- 2018/03/15
CRDT- 2018/03/16 06:00
PHST- 2018/01/30 00:00 [received]
PHST- 2018/03/11 00:00 [revised]
PHST- 2018/03/14 00:00 [accepted]
PHST- 2018/03/16 06:00 [entrez]
PHST- 2018/03/16 06:00 [pubmed]
PHST- 2018/08/29 06:00 [medline]
PHST- 2018/03/15 00:00 [pmc-release]
AID - molecules23030665 [pii]
AID - molecules-23-00665 [pii]
AID - 10.3390/molecules23030665 [doi]
PST - epublish
SO  - Molecules. 2018 Mar 15;23(3):665. doi: 10.3390/molecules23030665.