Optimization of a two-step process comprising lipase catalysis and thermal cyclizationimproves the efficiency of synthesis of six-membered cyclic carbonate from trimethylolpropane and dimethylcarbonate.
(2013) In Biotechnology Progress 29(1). p.66-73- Abstract
- Six-membered cyclic carbonates are potential monomers for phosgene and/or isocyanate free polycarbonates and polyurethanes via ring-opening polymerization. A two-step process for their synthesis comprising lipase-catalyzed transesterificationofa polyol, trimethylolpropane(TMP) with dimethylcarbonate(DMC)in a solvent-free system followed by thermal cyclization was optimized to improve process efficiency and selectivity. Using full factorial designed experiments and partial least squares (PLS) modeling for thereaction catalyzed by Novozym®435 (N435; immobilized Candida antarctica lipase B), the optimum conditions for obtaining either high proportion of mono-carbonated TMP and TMP-cyclic-carbonate (3 and 4), or di-carbonated TMP and... (More)
- Six-membered cyclic carbonates are potential monomers for phosgene and/or isocyanate free polycarbonates and polyurethanes via ring-opening polymerization. A two-step process for their synthesis comprising lipase-catalyzed transesterificationofa polyol, trimethylolpropane(TMP) with dimethylcarbonate(DMC)in a solvent-free system followed by thermal cyclization was optimized to improve process efficiency and selectivity. Using full factorial designed experiments and partial least squares (PLS) modeling for thereaction catalyzed by Novozym®435 (N435; immobilized Candida antarctica lipase B), the optimum conditions for obtaining either high proportion of mono-carbonated TMP and TMP-cyclic-carbonate (3 and 4), or di-carbonated TMP and monocarbonated TMP-cyclic-carbonate (5 and 6) were found. The PLS model predicted that the reactions using 15-20% (w/w) N435 at DMC:TMP molar ratio of 10-30 can reach about 65% total yield of 3 and 4 within 10 h, and 65-70% total yield of 5 and 6 within 32-37 h, respectively. High consistency between the predictedresults and empirical data was shown with 66.1% yield of 3 and 4 at 7 h and 67.4% yield of 5 and 6 at 35 h, using 18% (w/w) biocatalyst and DMC:TMPmolar ratio of20. Thermal cyclization of the product from 7 h reaction, at 110 °C in the presence of acetonitrile increased the overall yield of cyclic carbonate 4 from about 2% to more than 75%within 24 h.N435 was reused for 5 consecutive batches, 10 h each, to give 3+4 with a yield of about 65% in each run. © 2012 American Institute of Chemical Engineers Biotechnol. Prog., 2012. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/3219263
- author
- Bornadel, Amin LU ; Hatti-Kaul, Rajni LU ; Sörensen, Kent ; Lundmark, Stefan LU and Pyo, Sang-Hyun LU
- organization
- publishing date
- 2013
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Biotechnology Progress
- volume
- 29
- issue
- 1
- pages
- 66 - 73
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000314472200009
- pmid:23125051
- scopus:84873314705
- pmid:23125051
- ISSN
- 1520-6033
- DOI
- 10.1002/btpr.1662
- language
- English
- LU publication?
- yes
- id
- 5f95b142-e31b-4803-8b4a-550d2c0556de (old id 3219263)
- date added to LUP
- 2016-04-01 10:21:58
- date last changed
- 2022-01-25 22:30:03
@article{5f95b142-e31b-4803-8b4a-550d2c0556de,
abstract = {{Six-membered cyclic carbonates are potential monomers for phosgene and/or isocyanate free polycarbonates and polyurethanes via ring-opening polymerization. A two-step process for their synthesis comprising lipase-catalyzed transesterificationofa polyol, trimethylolpropane(TMP) with dimethylcarbonate(DMC)in a solvent-free system followed by thermal cyclization was optimized to improve process efficiency and selectivity. Using full factorial designed experiments and partial least squares (PLS) modeling for thereaction catalyzed by Novozym®435 (N435; immobilized Candida antarctica lipase B), the optimum conditions for obtaining either high proportion of mono-carbonated TMP and TMP-cyclic-carbonate (3 and 4), or di-carbonated TMP and monocarbonated TMP-cyclic-carbonate (5 and 6) were found. The PLS model predicted that the reactions using 15-20% (w/w) N435 at DMC:TMP molar ratio of 10-30 can reach about 65% total yield of 3 and 4 within 10 h, and 65-70% total yield of 5 and 6 within 32-37 h, respectively. High consistency between the predictedresults and empirical data was shown with 66.1% yield of 3 and 4 at 7 h and 67.4% yield of 5 and 6 at 35 h, using 18% (w/w) biocatalyst and DMC:TMPmolar ratio of20. Thermal cyclization of the product from 7 h reaction, at 110 °C in the presence of acetonitrile increased the overall yield of cyclic carbonate 4 from about 2% to more than 75%within 24 h.N435 was reused for 5 consecutive batches, 10 h each, to give 3+4 with a yield of about 65% in each run. © 2012 American Institute of Chemical Engineers Biotechnol. Prog., 2012.}},
author = {{Bornadel, Amin and Hatti-Kaul, Rajni and Sörensen, Kent and Lundmark, Stefan and Pyo, Sang-Hyun}},
issn = {{1520-6033}},
language = {{eng}},
number = {{1}},
pages = {{66--73}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Biotechnology Progress}},
title = {{Optimization of a two-step process comprising lipase catalysis and thermal cyclizationimproves the efficiency of synthesis of six-membered cyclic carbonate from trimethylolpropane and dimethylcarbonate.}},
url = {{http://dx.doi.org/10.1002/btpr.1662}},
doi = {{10.1002/btpr.1662}},
volume = {{29}},
year = {{2013}},
}