Base initiated depolymerization of polycarbonates to epoxide and carbon dioxide co-monomers: a computational study

Literature Information

Publication Date 2013-04-09
DOI 10.1039/C3GC40475G
Impact Factor 10.182
Authors

Donald J. Darensbourg, Andrew D. Yeung, Sheng-Hsuan Wei


View Original

Abstract

High-accuracy CBS-QB3(+) calculations were used to obtain the free energy barriers for several polycarbonates of interest to undergo alkoxide back-biting to give the corresponding epoxide and carbon dioxide. Free energy barriers to epoxide formation were modest for most polymeric alkoxides (12.7–17.4 kcal mol−1), and they were higher than for the same starting material to give cyclic carbonate (10.7–14.6 kcal mol−1). Poly(cyclopentene carbonate) differs: epoxide formation has a lower free energy barrier (13.3 kcal mol−1) than cyclic carbonate formation (19.9 kcal mol−1). These results explain why poly(cyclopentene carbonate) depolymerizes to cyclopentene oxide when treated with a strong base, whereas propylene and styrene polycarbonates depolymerize to their respective cyclic carbonates. Recycling via regeneration of the monomer represents the ideal method for producing material of the highest quality.

Related Literature

A theoretical study on quasi-one-dimensional open-shell singlet ladder oligomers: multi-radical nature, aromaticity and second hyperpolarizability

Kotaro Fukuda, Jun-ya Fujiyoshi, Hiroshi Matsui, Takanori Nagami, Shota Takamuku, Benoît Champagne

2017-03-06 Research Article

DOI: 10.1039/C7QO00108H

Manganese-mediated reductive amidation of esters with nitroarenes

Chi Wai Cheung, Ni Shen, Shao-Peng Wang, Asim Ullah, Xile Hu, Jun-An Ma

2019-01-30 Research Article

DOI: 10.1039/C8QO01405A

Guest-mediated chirality transfer in the host–guest complexes of an atropisomeric perylene bisimide cyclophane host‡

Meike Sapotta, Peter Spenst, Chantu R. Saha-Möller

2019-03-05 Research Article

DOI: 10.1039/C9QO00172G

Synthesis and structure revision of symplocin A

Lu-Ping Shao, Chang-Mei Si, Zhuo-Ya Mao, Wen Zhou, Tadeusz F. Molinski, Bang-Guo Wei, Guo-Qiang Lin

2017-02-09 Research Article

DOI: 10.1039/C7QO00052A

Ir-Catalyzed ring-opening of oxa(aza)benzonorbornadienes with water or alcohols

Xin Yang, Wen Yang, Yongqi Yao, Yingying Deng, Dingqiao Yang

2019-03-06 Research Article

DOI: 10.1039/C8QO01403E

Catalytic asymmetric substitution of ortho-hydroxybenzyl alcohols with tetronic acid-derived enamines: enantioselective synthesis of tetronic acid-derived diarylmethanes

Meng-Meng Xu, Hai-Qing Wang, Ying Wan, Guofeng He, Jingjing Yan, Shu Zhang, Shu-Liang Wang, Feng Shi

2016-12-12 Research Article

DOI: 10.1039/C6QO00549G

Dimerization of substituted 4-aryl-1,3-diacetylenes – quantum chemical calculations and kinetic studies

Alexandra Janiszewski, Jonas Fax, Gebhard Haberhauer

2019-02-26 Research Article

DOI: 10.1039/C9QO00119K

You might also like

Compound Q&A

What precautions should be taken when handling 4-Methyl-6-(trifluoromethyl)quinoline (CAS: 40716-16-3)?

When handling 4-Methyl-6-(trifluoromethyl)quinoline (CAS: 40716-16-3), safety go...

40716-16-34-Methyl-6-(trifluor...
Compound Q&A

What is 4-(3,5-Difluorophenyl)aniline (CAS: 405058-00-6)?

4-(3,5-Difluorophenyl)aniline is an aromatic organic compound with the CAS numbe...

405058-00-64-(3,5-Difluoropheny...
Compound Q&A

How is 5-{[4-(Trifluoromethyl)phenyl]sulfanyl}-1,2,3-thiadiazole-4-carboxylic acid (CAS: 338982-07-3) typically synthesized?

5-{[4-(Trifluoromethyl)phenyl]sulfanyl}-1,2,3-thiadiazole-4-carboxylic acid can ...

338982-07-35-{[4-(Trifluorometh...
Compound Q&A

What is the market or research trend for 4-Benzylaniline hydrochloride (CAS: 6317-57-3)?

The market for 4-Benzylaniline hydrochloride (CAS: 6317-57-3) is steadily growin...

6317-57-34-Benzylaniline hydr...
Compound Q&A

Is [3-(Diethylsulfamoyl)phenyl]boronic acid (CAS: 871329-58-7) safe?

[3-(Diethylsulfamoyl)phenyl]boronic acid is generally considered safe when handl...

871329-58-7[3-(Diethylsulfamoyl...
Compound Q&A

What are the main uses of 3-Bromo-2,5-dimethoxyaniline (CAS: 115929-62-9)?

3-Bromo-2,5-dimethoxyaniline is mainly used in the pharmaceutical and chemical i...

115929-62-93-Bromo-2,5-dimethox...
Compound Q&A

What regulatory guidelines apply to N-Methyl-1-(5-methyl-1H-indol-3-yl)methanamine (CAS: 915922-67-7)?

N-Methyl-1-(5-methyl-1H-indol-3-yl)methanamine (CAS: 915922-67-7) is subject to ...

915922-67-7N-Methyl-1-(5-methyl...
Compound Q&A

What industries use Carbamic acid, N-[(5S)-5,6-diamino-6-oxohexyl]-, 1,1-dimethylethyl ester (CAS: 24828-96-4)?

This compound is primarily used in the pharmaceutical industry for the synthesis...

24828-96-4Carbamic acid, N-[(5...
Compound Q&A

How should 2-Methyl-2-propanyl [(1S,3R)-3-aminocyclohexyl]carbamate (CAS: 1298101-47-9) be stored?

2-Methyl-2-propanyl [(1S,3R)-3-aminocyclohexyl]carbamate (CAS: 1298101-47-9) sho...

1298101-47-92-Methyl-2-propanyl ...
Compound Q&A

What industries use Ethyl 2-bromo-4,4,4-trifluorobutanoate (CAS: 367-33-9)?

Ethyl 2-bromo-4,4,4-trifluorobutanoate (CAS: 367-33-9) is utilized in the pharma...

367-33-9Ethyl 2-bromo-4,4,4-...

Source Journal

Green Chemistry

Green Chemistry
CiteScore: 16.1
Self-citation Rate: 7.5%
Articles per Year: 944

Green Chemistry provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on, but not limited to, the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998). Green chemistry is the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry is at the frontiers of this continuously-evolving interdisciplinary science and publishes research that attempts to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. Submissions on all aspects of research relating to the endeavour are welcome. The journal publishes original and significant cutting-edge research that is likely to be of wide general appeal. To be published, work must present a significant advance in green chemistry. Papers must contain a comparison with existing methods and demonstrate advantages over those methods before publication can be considered. For more information please see this Editorial. Coverage includes the following, but is not limited to: Design (e.g. biomimicry, design for degradation/recycling/reduced toxicity…) Reagents & Feedstocks (e.g. renewables, CO2, solvents, auxiliary agents, waste utilization…) Synthesis (e.g. organic, inorganic, synthetic biology…) Catalysis (e.g. homogeneous, heterogeneous, enzyme, whole cell…) Process (e.g. process design, intensification, separations, recycling, efficiency…) Energy (e.g. renewable energy, fuels, photovoltaics, fuel cells, energy storage, energy carriers…) Applications (e.g. electronics, dyes, consumer products, coatings, pharmaceuticals, preservatives, building materials, chemicals for industry/agriculture/mining…) Impact (e.g. safety, metrics, LCA, sustainability, (eco)toxicology…) Green chemistry is, by definition, a continuously-evolving frontier. Therefore, the inclusion of a particular material or technology does not, of itself, guarantee that a paper is suitable for the journal. To be suitable, the novel advance should have the potential for reduced environmental impact relative to the state of the art. Green Chemistry does not normally deal with research associated with 'end-of-pipe' or remediation issues.

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.