Furan Dicarboxylic Acid and Polyethylene Furanoate
Furan Dicarboxylic Acid and Polyethylene Furanoate
The biobased plastic that could replace polyethylene terephthalate
The Polymerist is a free newsletter that publishes twice a week with one in-depth article on Tuesdays and a roundup and honest analysis of what happened in the world of chemicals on Fridays. Join the subscriber list to get free updates with honest analysis from someone with a PhD in chemistry from the industry. Need a job or looking to fill a position? Check out the chemical industry jobs discussion thread!
In the News
Last December Avantium N.V. secured a €5.4 million grant from the Netherlands Enterprise Agency to be paid out in 16 tranches over four years for the construction of a furan dicarboxylic acid plant in Geleen, NL.
Avantium is trying to commercialize polyethylene furanoate otherwise known as PEF. A similar polymer to PEF that we use everyday is polyethylene terephthalate or PET— one of the big six plastics. Similar to PET the synthesis of PEF is based on a condensation polymerization of dimethyl furanoate and ethylene glycol. The key to getting to dimethyl furanoate is to make furan dicarboxlic acid, which is preferably derived from biomass as opposed to oil.
Avantium didn’t start out trying to commercialize PEF. They were spun off from Shell in 2000 with the idea of utilizing high throughput R&D for catalysis research with the aim of become a service driven business for the chemical industry.
During the first years of our existence, our strategic aim was to apply high-throughput technology across a range of applications and industries. We invested significant resources both to advance the technology we acquired when we separated from Shell and to develop new systems and associated software. After the inception period, Avantium decided to focus on providing high-throughput technology-based R&D services to companies in the chemical and pharmaceutical industries. In 2005 we started to also offer R&D systems to our customers, because customers had shown interest in applying our high-throughput techniques in their own laboratories.
Eventually Avantium would realize that their own research could enable a plant based plastics future and they embarked on the journey to commercialize polyethylene furanoate and furan dicarboxylic acid or as they call it YXY technology. This is a monumentally difficult task due to the low cost and similar properties of the plastic they are trying to compete with— polyethylene terephthalate. This is a real world example of what might be referred to as the “Nylon Problem.” I’ll write something about this the Nylon problem this year, but for now John Siddall talks about this in ACS Industry Matters better than I could right now.
Polyethylene Furanoate
The basics on polyethylene furanoate need a good starting point and this paper from Gandini and coworkers is a wonderful and open access place to start. They cite Moore and Kelly as the pioneers of furan based polyesters because they were the chemists to report on these polymers back in 1977 in Macromolecules. I conducted my PhD research in Moore’s old laboratory at Rensselaer Polytechnic Institute and his office was the down the hall. Sadly, James Moore died on December 31, 2017 at the age of 78. We would chat occasionally during my time at RPI in 2016 about research, synthetic chemistry, and making polymers. Moore and Kelly were the first to report the synthesis of furan based polyesters with furan dicarboxylic acid, 1,6 hexane diol, and a furan based diol. Polyethylene terephthalate was commercialized in the 1950s under the trade name Mylar and the first PET bottle was patented in 1973—both by DuPont.
It might further help to put into context what was going on in the 1970s. In 1973 the oil embargo from the Saudi Oil Producing Exporting Countries started due to the US supporting Israel. The oil embargo would stop in 1974, but the shock of gas lines and rationing of gasoline in the mid 1970s must have made chemists think “we should make chemicals some other way.” The concept of oil being a finite resource and that we could run out was a real fear, it still is to some extent, but making plastics in the 1970s from biomass seemed like a good idea. Moore and Kelly were just about 40-50 years too early and ahead of their time.
Gandini and coworkers synthesized their PET analogue using furan dicarboxylic acid (FDCA) and ethylene glycol shown in the scheme below to produce polyethylene furanoate. This work in 2008 showed that it was possible to synthesize polyethylene furanoate (PEF).
There was additional follow-up by other research groups, most notably my own with my fellow graduate student at the time Jianhui Zhu. Zhu and coworkers would publish the synthesis and properties polybutylene furanoate (PBF) in Macromolecules in 2013. In my talks with Jianhui when we were both graduate students there were not as many papers as you would expect being published on furan based polyesters at the time primarily because no one could get furan dicarboxylic acid (FDCA) in any meaningful quantities or if there was FDCA it was extremely expensive.
Even now in 2020 FDCA is not that affordable through typical chemical catalogues that academics might use. Fischer Scientific has one of the lower prices for FDCA that I could find at $175 for 25 grams. In order to make PEF or PBF or any furan based polyester having control of the synthesis of the FDCA would be critical in controlling the supply, pricing, and application of polyesters. Small scale reactions for something like this might be around 100 grams if you want to use mechanical stirring due to the high viscosity of the melt condensation polymerization (think about making caramel, but way way thicker).
Furan Dicarboxylic Acid—Controlling The Supply Chain
Researchers at Avantium probably already knew it was possible to synthesize PEF before Gandini and coworkers published and their early patents on making furan dicarboxylic acid go back to 2006. As Moore and Kelly had noted the best way to make furan dicarboxylic acid was to oxidize sugars such as sucrose or glucose to 5-hydroxyfurfural and then further oxidation to furan dicarboxylic acid. From the Furanix patent on making 5-hydroxymethylfural ether derivatives:
the application of the products of the method of the present invention, i.e. the ethers, is in the use as a fuel or fuel additive and as precursor for the manufacture of 2,5-di(hydroxymethyl)furan, furan-2,5-dicarboxylic acid, 2-hydroxymethylfuran-5-carboxylic acid, 2,5-(dihydroxymethyl)tetrahydrofuran, which can be used as monomers in a polymerisation process, optionally after conversion of the diol to a diamine. See for a review Moreau, Topics in catalysis, 2004, 27, 11-30.
The idea of a company starting up the production of a completely new polymer with a whole different feedstock that was not oil based back in 2005 seemed like a relatively good idea because oil prices were climbing every year and would eventually peak in 2008 and then again in 2014. Avantium would sell off parts of its business and eventually formed a JV with BASF to create smaller subsidiaries where BASF was the majority owner. From Avatium’s 2016 annual report:
Within the consolidated Avantium N.V., the entities involved in the trans - action are YXY Technologies B.V. and Furanix Technologies B.V. BASF holds a 51% share of the JV, where Avantium holds the remaining 49%. On 23 September 2016 the Joint Venture agreement was signed, and the new company name Synvina revealed, which was established in the Netherlands on 30 November 2016.
From about 2016-2019 I imagine the business case for furan technology was constantly in doubt despite the strong environmental case that it should be done. Oil prices tanked in 2016 and anything biobased that made sense with high oil prices (i.e. algal biofuels) made less sense with the advent of fracking, oversupply of oil, and low prices. I think Avantium sought to de-risk and raise capital by doing the JV with BASF in 2016. For BASF the big risk was probably impatient shareholders while the regulatory frameworks were put into place and construction of the demonstration plants could be finished. Best case scenario for BASF would be they get early access to a technology that might change the plastics industry. BASF could theoretically start development work on applications of PEF and furan based plastics well before anyone else and develop their own IP in the event the technology reached global scale.
I think from the intellectual property side there was relatively little risk for BASF and Avantium aside from their patents expiring. I am not a lawyer so this is not a legal conclusion or a legal opinion. I believe that since Moore and Kelly reported a polyethylene furanoate synthesis back in the 1970s it is obvious to one skilled in the art of polyester synthesis that making PEF could be achieved through similar techniques to that of PET. Gandini and coworkers did it in 2008 for PEF and Zhu and coworkers did it in 2013 for PBF. Thus, the only commercial way to control who gets to make furan based polyesters is to have the most economical way to make furan dicarboxylic acid. The patents Avantium filed in 2006 are set to expire in 2029.
If you can control who gets to make furan dicarboxylic acid you can control the whole downstream process of who gets to make furan based polyesters. If you can control the supply of FDCA you can return money to your investors (shareholders) ideally with a profit and you can do good in the world by making a plastic from biomass feedstocks. Winning in the business of polymer chemistry is in part who can get the monomers at the lowest cost and finding high value applications of the resulting polymer/plastic.
In 2019 Avantium would buy out BASF in the joint ventures and retake full control:
In the Netherlands, Avantium N.V. has announced that it has retaken full ownership of its YXY plants-to-plastics technology through the purchase of BASF’s shares in the Synvina joint venture. Furthermore, the company has appointed Dr Marcel Lubben as Managing Director of Synvina to lead the commercialization of the YXY technology, effective February 1, 2019.
Avantium is a publicly traded company based in the Netherlands and trades under the symbol AVTXF on the AMS exchange. To date the company has not yielded positive cashflow, but they are in the process of scaling their technology.
In Conclusion
If we were going to see any of the big six plastics get replaced or get market share taken away it is going to be by PEF going after PET market share. Avantium already has major consumer packaged goods companies such as Danone and Carlsberg as partners to commercialize PEF based food packaging. If we are going to see true adoption of PEF in the world then subsidizing the monomer and polymer synthesis is one way a government can help transition plastics and chemicals away from petroleum feedstocks.
Thus, the €5.4 million grant from the Netherlands to Avantium for construction of an FDCA plant is the government signaling that this technology is important for the future. If you read part 1 and part 2 of the “solving the plastic waste problem” series then you should know that most of our plastics and polymers economy was developed by scientists in the chemical industry from the early 1900s to about the 1960s. One thing that I have alluded to in the past is that the monomer synthesis or obtaining the raw material at economical prices is one of the more difficult things to overcome, especially now with low oil prices and minimal demand on refined products like gasoline.
I haven’t written about nylon yet, but at the time of nylon’s invention the fabric of choice was silk. You get silk from the silk worm cocoon and it is a natural polyamide. The high cost of silk meant that pretty much any new synthetic method to create a polymer with similar or near similar properties to that of silk would automatically become economically viable because making nylons in a chemical plant was always going to be more economical than harvesting it from a silk worm cocoon.
This is not the case for furan based polyesters. Starting up these FDCA and PEF plants under an environment where there is a strong economical case for the incumbent requires the investment by public entities such as governments. I wish the Avantium team the best of luck for the 2020s and look forward to seeing PEF bottles on the shelves.
Tony
If you have any tips email me at polymerist@substack.com
The views here are my own and do not represent those of my employer nor should they be considered investment advice.
This is also all provided to you free of charge so pay me back by subscribing and/or sharing with your friends and coworkers who are chemically inclined. Have any strong opinions? Let me know in the comments or just reply to this email.
