Abstract
A series of spray dried zeolitic imidazolate frameworks (ZIFs = ZIF-8, ZIF-67, and Zn/Co-ZIF) are used as a catalyst for the bulk ring-opening polymerization of δ-valerolactone without any co-catalyst to generate polyvalerolactone. Interestingly, using the same catalyst under the same reaction conditions could manipulate the structure of the product polymer, and thus its physical properties. Thus, using a dried substrate leads to the formation of the cyclic polymer while a linear polymer was formed on using the commercially available substrate. An activated monomer mechanism has been suggested where the propagating zinc alkoxide undergoes an intramolecular transesterification to release cyclic or linear polyvalerolactone. The ROP of δ-VL without drying shows that the polymeric zwitterions have little tendency to cyclize in the presence of moisture. At 140 °C, ZIF-8 shows a superior catalytic activity resulting in the production of cyclic polyvalerolactone having a high molecular weight as compared to ZIF-67 or Zn/Co-ZIF due to the presence of highly active sites. The catalyst could be recycled and reused without any significant loss of catalytic activity.
| Original language | English |
|---|---|
| Article number | e4890 |
| Journal | Applied Organometallic Chemistry |
| Volume | 33 |
| Issue number | 5 |
| DOIs | |
| Publication status | Published - 1 May 2019 |
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Keywords
- biodegradable polymer
- heterogeneous catalyst
- Polyvalerolactone
- ring opening polymerization
- Zeolitic imidiazolate framework
ASJC Scopus subject areas
- Chemistry(all)
- Inorganic Chemistry
Cite this
Switching from linear to cyclic δ-Polyvalerolactone synthesized via zeolitic imidazolate framework as a catalyst : A promising approach. / Naz, Farah; Mousavi, Bibimaryam; Luo, Zhixiong; Jabbour, Christia; Heynderickx, Philippe M.; Chaemchuen, Somboon; Verpoort, Francis.
In: Applied Organometallic Chemistry, Vol. 33, No. 5, e4890, 01.05.2019.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Switching from linear to cyclic δ-Polyvalerolactone synthesized via zeolitic imidazolate framework as a catalyst
T2 - A promising approach
AU - Naz, Farah
AU - Mousavi, Bibimaryam
AU - Luo, Zhixiong
AU - Jabbour, Christia
AU - Heynderickx, Philippe M.
AU - Chaemchuen, Somboon
AU - Verpoort, Francis
PY - 2019/5/1
Y1 - 2019/5/1
N2 - A series of spray dried zeolitic imidazolate frameworks (ZIFs = ZIF-8, ZIF-67, and Zn/Co-ZIF) are used as a catalyst for the bulk ring-opening polymerization of δ-valerolactone without any co-catalyst to generate polyvalerolactone. Interestingly, using the same catalyst under the same reaction conditions could manipulate the structure of the product polymer, and thus its physical properties. Thus, using a dried substrate leads to the formation of the cyclic polymer while a linear polymer was formed on using the commercially available substrate. An activated monomer mechanism has been suggested where the propagating zinc alkoxide undergoes an intramolecular transesterification to release cyclic or linear polyvalerolactone. The ROP of δ-VL without drying shows that the polymeric zwitterions have little tendency to cyclize in the presence of moisture. At 140 °C, ZIF-8 shows a superior catalytic activity resulting in the production of cyclic polyvalerolactone having a high molecular weight as compared to ZIF-67 or Zn/Co-ZIF due to the presence of highly active sites. The catalyst could be recycled and reused without any significant loss of catalytic activity.
AB - A series of spray dried zeolitic imidazolate frameworks (ZIFs = ZIF-8, ZIF-67, and Zn/Co-ZIF) are used as a catalyst for the bulk ring-opening polymerization of δ-valerolactone without any co-catalyst to generate polyvalerolactone. Interestingly, using the same catalyst under the same reaction conditions could manipulate the structure of the product polymer, and thus its physical properties. Thus, using a dried substrate leads to the formation of the cyclic polymer while a linear polymer was formed on using the commercially available substrate. An activated monomer mechanism has been suggested where the propagating zinc alkoxide undergoes an intramolecular transesterification to release cyclic or linear polyvalerolactone. The ROP of δ-VL without drying shows that the polymeric zwitterions have little tendency to cyclize in the presence of moisture. At 140 °C, ZIF-8 shows a superior catalytic activity resulting in the production of cyclic polyvalerolactone having a high molecular weight as compared to ZIF-67 or Zn/Co-ZIF due to the presence of highly active sites. The catalyst could be recycled and reused without any significant loss of catalytic activity.
KW - biodegradable polymer
KW - heterogeneous catalyst
KW - Polyvalerolactone
KW - ring opening polymerization
KW - Zeolitic imidiazolate framework
UR - http://www.scopus.com/inward/record.url?scp=85064574868&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85064574868&partnerID=8YFLogxK
U2 - 10.1002/aoc.4890
DO - 10.1002/aoc.4890
M3 - Article
AN - SCOPUS:85064574868
VL - 33
JO - Applied Organometallic Chemistry
JF - Applied Organometallic Chemistry
SN - 0268-2605
IS - 5
M1 - e4890
ER -