Sustainable polymers
Lead Research Organisation:
University of York
Department Name: Chemistry
Abstract
Over 90% of bulk polymers with a production volume of greater than 150 million tonnes per annum are sourced from crude oil. Within the UK, the polymers industry directly employs 286,000 people and has annual sales of £18.1 billion which accounts for 2.1% of UK GDP. It produces around 2.5 million tonnes of polymer every year and is achieving an annual growth of 2.5%. The UK is in the top 5 polymer producers in the EU and its exports are worth £4.6 billion to the UK economy.
These polymers are ubiquitous in everyday life and have many applications including: medical, transport, electrical, construction and packaging; the latter accounting for over a third of all polymers produced. This dependence on petrochemicals for polymer production has environmental and economic risks and will, ultimately, become unsustainable as supplies of crude oil become exhausted. Therefore, there are good reasons to develop new processes for polymer production using renewable resources and for the UK, such resources must not compete with food production. Carbon dioxide is a particularly promising renewable resource, especially the use of waste carbon dioxide from sources such as power stations, chemical plants, cement and metal works.
The overall aim of this project is to develop the chemistry and engineering required to transform waste biomass and carbon dioxide into commodity polymers (2011 global production 280 million metric tonnes), specifically: polyalkanes, polyethers, polyesters, polycarbonates and polyurethanes. The key reaction pathway is from biomass to alkenes (polymerizable to polyalkanes) to epoxides which can be polymerized to polyethers or copolymerized to produce polyesters or polycarbonates. These can be further reacted to produce polyurethanes suitable for applications in furniture, insulation and adhesives. For this to be sustainable, the alkene and other reactants must also be sustainably sourced and we will investigate the use of terpenes, sugar derivatives and unsaturated acid derivatives obtained from agricultural and forestry waste. For example, during the 2011-2012 growing season, the EU processed 1.9 million metric tonnes of citrus producing approximately 950,000 metric tonnes of waste. After removal of water this left 190,000 metric tonnes of residue from which about 14,000 metric tonnes of limonene could be isolated for use as a polymer feedstock. In addition to carrying out the required chemical research, the engineering necessary to scale up the syntheses to pilot plant and production scale will be carried out.
The chemical and mechanical processes associated with isolating materials from biomass and converting them into polymers will inevitably require energy and other chemicals, the production of which will generate carbon dioxide. Therefore, lifecycle analysis will be used to determine all of the carbon dioxide emissions associated with polymer production from both petrochemical and biomass sources. Comparison of the data will provide a quantitative understanding of how much better the sustainable route is than the petrochemical route and will illustrate which aspects of the synthesis are responsible for most of the carbon dioxide emissions. This, combined with energy usage and cost data will allow the project team to concentrate their efforts on minimising these emissions through for example the use of microwave heating rather than conventional heating and the use of alternative solvents such as supercritical carbon dioxide.
In summary, polymers are ubiquitous in everyday life and the polymer industry is a major UK employer. Their scale of production and range of applications means that they are a high priority target to switch from fossil to sustainable sourcing. Successful completion of this project will protect UK jobs, protect the UK supply of these essential materials and provide income through license agreements with overseas manufacturers.
These polymers are ubiquitous in everyday life and have many applications including: medical, transport, electrical, construction and packaging; the latter accounting for over a third of all polymers produced. This dependence on petrochemicals for polymer production has environmental and economic risks and will, ultimately, become unsustainable as supplies of crude oil become exhausted. Therefore, there are good reasons to develop new processes for polymer production using renewable resources and for the UK, such resources must not compete with food production. Carbon dioxide is a particularly promising renewable resource, especially the use of waste carbon dioxide from sources such as power stations, chemical plants, cement and metal works.
The overall aim of this project is to develop the chemistry and engineering required to transform waste biomass and carbon dioxide into commodity polymers (2011 global production 280 million metric tonnes), specifically: polyalkanes, polyethers, polyesters, polycarbonates and polyurethanes. The key reaction pathway is from biomass to alkenes (polymerizable to polyalkanes) to epoxides which can be polymerized to polyethers or copolymerized to produce polyesters or polycarbonates. These can be further reacted to produce polyurethanes suitable for applications in furniture, insulation and adhesives. For this to be sustainable, the alkene and other reactants must also be sustainably sourced and we will investigate the use of terpenes, sugar derivatives and unsaturated acid derivatives obtained from agricultural and forestry waste. For example, during the 2011-2012 growing season, the EU processed 1.9 million metric tonnes of citrus producing approximately 950,000 metric tonnes of waste. After removal of water this left 190,000 metric tonnes of residue from which about 14,000 metric tonnes of limonene could be isolated for use as a polymer feedstock. In addition to carrying out the required chemical research, the engineering necessary to scale up the syntheses to pilot plant and production scale will be carried out.
The chemical and mechanical processes associated with isolating materials from biomass and converting them into polymers will inevitably require energy and other chemicals, the production of which will generate carbon dioxide. Therefore, lifecycle analysis will be used to determine all of the carbon dioxide emissions associated with polymer production from both petrochemical and biomass sources. Comparison of the data will provide a quantitative understanding of how much better the sustainable route is than the petrochemical route and will illustrate which aspects of the synthesis are responsible for most of the carbon dioxide emissions. This, combined with energy usage and cost data will allow the project team to concentrate their efforts on minimising these emissions through for example the use of microwave heating rather than conventional heating and the use of alternative solvents such as supercritical carbon dioxide.
In summary, polymers are ubiquitous in everyday life and the polymer industry is a major UK employer. Their scale of production and range of applications means that they are a high priority target to switch from fossil to sustainable sourcing. Successful completion of this project will protect UK jobs, protect the UK supply of these essential materials and provide income through license agreements with overseas manufacturers.
Planned Impact
Major beneficiaries of this research will be the UK polymers industry which directly employs 286,000 people and has sales of £18.1 billion pa (2.1% of UK GDP). Over 80% of commercially produced chemicals are polymers and their production consumes 8% of the oil/gas extracted each year. Polymer manufacturers will benefit from the availability of technology which produces polymers from non-petrochemical feedstocks, thus opening new supply chains and sustainable revenue streams as petrochemical resources become increasingly scarce. One of the waste feedstocks is CO2, so the project will turn CO2 from a waste product into a valuable resource to enhance the wealth generating capacity of UK industry. To facilitate the transfer of the technology to these industrial sectors, the project has an Industrial Advisory Board whose members are drawn from polymer related industries (Lotte, Econic, Plaxica, Bayer). The IAB members were involved in defining the scope of this proposal and will also ensure that the research undertaken during the project is that which is most suited for commercialisation.
The polymers industry supplies a vast range of other industries including those in medical, transport, electrical, construction and packaging sectors. Thus, many other UK companies rely on the polymer industry. This proposal will therefore protect the jobs and wealth creation associated with these industries. Ultimately, these goods are used by UK consumers, so the entire UK population will benefit from sustainably sourced polymer containing products by having their quality of life and standard of living preserved. The UK government has legally binding commitments to reduce the UK's CO2 emissions. Whilst utilization of CO2 in chemicals production can only consume a very small percentage of the UK's CO2 emissions, this can be a very profitable thing to do. For example, the polyether needed to prepare current polyurethanes is prepared from propylene oxide which at commercial rates costs $2,000 per tonne. By replacing the polyether with a polycarbonate, up to 40% of the propylene oxide can be replaced by CO2, resulting in a cost saving of ca $800 per tonne. The revenue raised by utilizing a small percentage of the CO2 in this way can then be used to partially offset the costs associated with carbon capture and storage for the remaining CO2. In addition, the current production of polymers from petrochemicals produces large amounts of waste CO2 and this project aims to reduce these emissions by at least 50%.
Another impact of this proposal will be on supply security by moving from internationally acquired oil to native waste (both CO2 and biomass). CO2 and biomass waste will be available for the foreseeable future, but global production of crude oil is expected to peak within the next 40 years. The UK government's very recent decision (17 July 2013) to phase out subsidies for biomass burning over the next ten years also makes this a very timely proposal as much more waste biomass will now be available and its conversion into high value chemicals will become a more attractive option. There will also be impacts on the environment and safety due to reductions in the amount of oil having to be transported across oceans etc.
There will be a significant impact on the future careers of the six PDRAs recruited to carry out this project as they will be ideally placed to continue work in this highly multidisciplinary area. The project will also have an impact on the academic careers of the PI/CIs by leaving them ideally placed to carry out similar work targeted at other commercial products and/or using other sustainable resources in the future. Finally, there is an impact to EPSRC itself which is under pressure from the UK government to fund research which is of commercial value to the UK. This project falls firmly in that area and the applicants will work with EPSRC to highlight this through articles on the EPSRC web site and in EPSRC newsletters.
The polymers industry supplies a vast range of other industries including those in medical, transport, electrical, construction and packaging sectors. Thus, many other UK companies rely on the polymer industry. This proposal will therefore protect the jobs and wealth creation associated with these industries. Ultimately, these goods are used by UK consumers, so the entire UK population will benefit from sustainably sourced polymer containing products by having their quality of life and standard of living preserved. The UK government has legally binding commitments to reduce the UK's CO2 emissions. Whilst utilization of CO2 in chemicals production can only consume a very small percentage of the UK's CO2 emissions, this can be a very profitable thing to do. For example, the polyether needed to prepare current polyurethanes is prepared from propylene oxide which at commercial rates costs $2,000 per tonne. By replacing the polyether with a polycarbonate, up to 40% of the propylene oxide can be replaced by CO2, resulting in a cost saving of ca $800 per tonne. The revenue raised by utilizing a small percentage of the CO2 in this way can then be used to partially offset the costs associated with carbon capture and storage for the remaining CO2. In addition, the current production of polymers from petrochemicals produces large amounts of waste CO2 and this project aims to reduce these emissions by at least 50%.
Another impact of this proposal will be on supply security by moving from internationally acquired oil to native waste (both CO2 and biomass). CO2 and biomass waste will be available for the foreseeable future, but global production of crude oil is expected to peak within the next 40 years. The UK government's very recent decision (17 July 2013) to phase out subsidies for biomass burning over the next ten years also makes this a very timely proposal as much more waste biomass will now be available and its conversion into high value chemicals will become a more attractive option. There will also be impacts on the environment and safety due to reductions in the amount of oil having to be transported across oceans etc.
There will be a significant impact on the future careers of the six PDRAs recruited to carry out this project as they will be ideally placed to continue work in this highly multidisciplinary area. The project will also have an impact on the academic careers of the PI/CIs by leaving them ideally placed to carry out similar work targeted at other commercial products and/or using other sustainable resources in the future. Finally, there is an impact to EPSRC itself which is under pressure from the UK government to fund research which is of commercial value to the UK. This project falls firmly in that area and the applicants will work with EPSRC to highlight this through articles on the EPSRC web site and in EPSRC newsletters.
Publications
Lim J
(2019)
Isoselective Lactide Ring Opening Polymerisation using [2]Rotaxane Catalysts
in Angewandte Chemie
Durkin A
(2019)
Scale-up and Sustainability Evaluation of Biopolymer Production from Citrus Waste Offering Carbon Capture and Utilisation Pathway.
in ChemistryOpen
Rehman A
(2019)
Kinetics and mechanistic investigation of epoxide/CO2 cycloaddition by a synergistic catalytic effect of pyrrolidinopyridinium iodide and zinc halides
in Journal of Energy Chemistry
Pankhurst JR
(2019)
Polynuclear alkoxy-zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO2.
in Dalton transactions (Cambridge, England : 2003)
Stößer T
(2019)
Easy access to oxygenated block polymers via switchable catalysis.
in Nature communications
Rehman A
(2019)
Highly selective, sustainable synthesis of limonene cyclic carbonate from bio-based limonene oxide and CO2: A kinetic study
in Journal of CO2 Utilization
Cooper N
(2019)
Linear estimators of biomass yield maps for improved biomass supply chain optimisation
in Applied Energy
Yi N
(2019)
Orthogonal functionalization of alternating polyesters: selective patterning of (AB) n sequences.
in Chemical science
Pellis A
(2019)
Enzymatic synthesis of unsaturated polyesters: functionalization and reversibility of the aza-Michael addition of pendants
in Polymer Chemistry
Zhu Y
(2019)
Metabolically Active, Fully Hydrolysable Polymersomes.
in Angewandte Chemie (International ed. in English)
Zhu Y
(2019)
Metabolically Active, Fully Hydrolysable Polymersomes
in Angewandte Chemie
Trott G
(2019)
Heterodinuclear zinc and magnesium catalysts for epoxide/CO 2 ring opening copolymerizations
in Chemical Science
Blanpain A
(2019)
Rapid Ring-Opening Metathesis Polymerization of Monomers Obtained from Biomass-Derived Furfuryl Amines and Maleic Anhydride.
in ChemSusChem
Laybourn A
(2019)
Combining continuous flow oscillatory baffled reactors and microwave heating: Process intensification and accelerated synthesis of metal-organic frameworks
in Chemical Engineering Journal
Raman SK
(2020)
Ti(IV)-Tris(phenolate) Catalyst Systems for the Ring-Opening Copolymerization of Cyclohexene Oxide and Carbon Dioxide.
in Organometallics
Little A
(2020)
Effects of Methyl Branching on the Properties and Performance of Furandioate-Adipate Copolyesters of Bio-Based Secondary Diols.
in ACS sustainable chemistry & engineering
Sulley GS
(2020)
Switchable Catalysis Improves the Properties of CO2-Derived Polymers: Poly(cyclohexene carbonate-b-e-decalactone-b-cyclohexene carbonate) Adhesives, Elastomers, and Toughened Plastics.
in Journal of the American Chemical Society
Deacy AC
(2020)
Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides.
in Nature chemistry
Carrodeguas L
(2020)
High elasticity, chemically recyclable, thermoplastics from bio-based monomers: carbon dioxide, limonene oxide and e-decalactone
in Green Chemistry
Chen T
(2020)
Bio-based and Degradable Block Polyester Pressure-Sensitive Adhesives
in Angewandte Chemie
Deacy AC
(2020)
Heterodinuclear complexes featuring Zn(ii) and M = Al(iii), Ga(iii) or In(iii) for cyclohexene oxide and CO2 copolymerisation.
in Dalton transactions (Cambridge, England : 2003)
Chen TTD
(2020)
Bio-based and Degradable Block Polyester Pressure-Sensitive Adhesives.
in Angewandte Chemie (International ed. in English)
Gregory GL
(2020)
Triblock polyester thermoplastic elastomers with semi-aromatic polymer end blocks by ring-opening copolymerization.
in Chemical science
Lie Y
(2020)
Work-hardening Photopolymer from Renewable Photoactive 3,3'-(2,5-Furandiyl)bisacrylic Acid.
in ChemSusChem
Rehman A
(2021)
Kinetic study for styrene carbonate synthesis via CO2 cycloaddition to styrene oxide using silica-supported pyrrolidinopyridinium iodide catalyst
in Journal of CO2 Utilization
Mukhtar Gunam Resul MF
(2021)
Development of rapid and selective epoxidation of a-pinene using single-step addition of H2O2 in an organic solvent-free process.
in RSC advances
Rehman A
(2021)
Synthesis of trans-limonene bis-epoxide by stereoselective epoxidation of (R)-(+)-limonene
in Journal of Environmental Chemical Engineering
Rehman A
(2021)
Recent advances in the synthesis of cyclic carbonates via CO2 cycloaddition to epoxides
in Journal of Environmental Chemical Engineering
Resul M
(2022)
Continuous process for the epoxidation of terpenes using mesoscale oscillatory baffled reactors
in Chemical Engineering and Processing - Process Intensification
Rehman A
(2022)
A Stereoselective Route to R-(+)-Limonene-Based Non-isocyanate Poly(hydroxyurethanes)
in Journal of Polymers and the Environment
Eze V
(2022)
Synthesis of cyclic a-pinane carbonate - a potential monomer for bio-based polymers
in RSC Advances
Usman M
(2023)
Synthesis of cyclic carbonates from CO2 cycloaddition to bio-based epoxides and glycerol: an overview of recent development.
in RSC advances
Mukhtar Gunam Resul M
(2023)
Recent advances in catalytic and non-catalytic epoxidation of terpenes: a pathway to bio-based polymers from waste biomass
in RSC Advances
Fernández A
(2023)
Environment-friendly epoxidation of limonene using tungsten-based polyoxometalate catalyst
in Molecular Catalysis
Description | Biome Technologies plc |
Amount | £14,000 (GBP) |
Organisation | Biome Technologies plc |
Sector | Private |
Country | United Kingdom |
Start | 08/2015 |
End | 10/2015 |
Description | Biome Technologies plc |
Amount | £9,070 (GBP) |
Organisation | Biome Technologies plc |
Sector | Private |
Country | United Kingdom |
Start | 04/2015 |
End | 05/2015 |
Description | Departmental Small Equipment Grant - FlowSyn Flow Reactor |
Amount | £16,183 (GBP) |
Organisation | University of York |
Sector | Academic/University |
Country | United Kingdom |
Start | 03/2015 |
End | 07/2015 |
Description | Dr. Alexandra Inayat - Leopoldina Postdoctoral Fellowship |
Amount | € 86,400 (EUR) |
Funding ID | LPDS 2015-03 |
Organisation | German Academy of Sciences |
Sector | Academic/University |
Country | Germany |
Start | 08/2015 |
End | 07/2017 |
Description | Dr. Naguib Ibrahim Mohamed Mohamed - Newton-Mosharafa Fund |
Amount | £11,000 (GBP) |
Organisation | British Council |
Sector | Charity/Non Profit |
Country | United Kingdom |
Start | 06/2015 |
End | 11/2015 |
Description | Dr. Yinjuan Bai - Special Projects for the Western Region |
Amount | £12,000 (GBP) |
Organisation | University of Leeds |
Department | China Scholarship Council |
Sector | Academic/University |
Country | United Kingdom |
Start | 12/2015 |
End | 12/2016 |
Description | Erwin Schroedinger Fellowship |
Amount | € 160,210 (EUR) |
Funding ID | J 4014-N34 |
Organisation | Austrian Science Fund (FWF) |
Sector | Academic/University |
Country | Austria |
Start | 10/2017 |
End | 09/2020 |
Description | Industrial Biotechnology Catalyst Grant - Round 4 |
Amount | £740,450 (GBP) |
Funding ID | BB/N023595/1 |
Organisation | Biotechnology and Biological Sciences Research Council (BBSRC) |
Sector | Public |
Country | United Kingdom |
Start | 07/2016 |
End | 06/2019 |
Description | Ministry of Education, Malaysia PhD Funding |
Amount | £75,000 (GBP) |
Organisation | Ministry of Higher Education (Malaysia) |
Sector | Public |
Country | Malaysia |
Start | 01/2015 |
End | 12/2017 |
Description | University of Engineering and Technology, Lahore PhD Funding |
Amount | £75,000 (GBP) |
Organisation | University of Engineering and Technology, Lahore |
Sector | Academic/University |
Country | Pakistan |
Start | 04/2015 |
End | 03/2018 |
Description | New Bio-based Monomers from Platform Molecules |
Organisation | University of California, Davis |
Department | Department of Chemistry |
Country | United States |
Sector | Academic/University |
PI Contribution | We received samples of new bio-derived monomers and used them in the synthesis of novel bio-derived polymers. The polymers where extensively analysed and their physical properties determined. The study is ongoing as other new monomers are produced and applied to polymerisations. |
Collaborator Contribution | Prof. Mark Mascal (UC Davis) has developed routes to a range of novel monomers from bio-derived platform molecules, and as part of this collaboration sent samples of the new monomers to the University of York for testing to polymerisations. Prof. Mascal has also assisted in the preparation of research articles following this study. |
Impact | Research article: ChemSusChem, 2017, 10,166 -170 |
Start Year | 2015 |