New Process to Develop Bio-based Polyamide Using Terpenes

The Fraunhofer Institute for Interfacial Engineering and Biotechnology IGB is using a new, recently patented process to develop new polyamides from the terpene 3-carene, a residual material from the cellulose industry. The biobased polyamides Caramid-R® and Caramid-S® produced using this process represent a new class of polyamides with outstanding thermal properties. The production of the monomer for Caramid-S® was already successfully piloted in a 100-liter scale. The Fraunhofer researchers are presenting the new polyamides at the K trade fair (Hall 7.0, Stand SC01).

From Wood Waste to High-performance Polymers

The Fraunhofer Institute for Interfacial Engineering and Biotechnology IGB has developed a sustainable alternative to petrochemically produced plastics using terpenes found in resin-rich wood. The natural substances are available from conifers such as pine, larch or spruce. In the production of pulp, in which wood is broken down to separate the cellulose fibers, the terpenes are isolated in large quantities as a by-product, turpentine oil.

In the joint project “TerPa – Terpenes as building blocks for biobased polyamides” funded by the German Federal Ministry of Food and Agriculture (BMEL) through the German Agency for Renewable Resources (FNR), researchers of Fraunhofer IGB, Bio, Electro and Chemocatalysis BioCat, Straubing branch have succeeded in optimizing the synthesis of lactams from 3-carene and the subsequent polymerization to Caramid-R® and Caramid-S®, representatives of a new class of terpene-based polyamides. Recently, a patent was granted for the synthesis process of the new polyamides from terpenes.

One-pot Reaction Scale-up to 100 Liters

The conversion of 3-carene to the corresponding lactam is possible in four successive chemical reactions that require neither complex production facilities nor expensive reagents. The key steps to the polymer building blocks 3S- and 3R-caranlactam are the selective production of the intermediate 3S-caranketone and its selective rearrangement to the isomeric 3R-caranketone.

The special feature is that the conversions can take place as a one-vessel reaction sequence in a single reactor. "This offers the possibility to produce the lactams also in simple plants without a complex reactor cascade. It is not necessary to purify the intermediate products," explains Paul Stockmann, who developed and optimized the promising process.

The synthesis of the monomer for Caramid-S® has now been scaled to the 100-liter scale at the Fraunhofer Center for Chemical-Biotechnological Processes CBP, the Leuna branch of Fraunhofer IGB. "In this pilot production, we produced several kilograms of monomer, which allows the polymerization to be scaled to the kilogram scale," says Dr. Harald Strittmatter, who heads the TerPa project.

Excellent Thermal Properties

The chemical structure of the natural substance 3-carene, which has barely been used commercially to date and would be very difficult to access from petrochemical feedstocks, leads to new polyamides that contain cyclic structures along the polymer chain. Due to these rings and other substituents, Caramid-S® and Caramid-R® have exceptional thermal properties compared to standard polyamides: The softening temperatures (glass transition) are above 110 °C.

Caranlactams Expand Functional Properties Of Standard Polyamides
In addition, the scientists have converted the biobased lactams to copolymers with other commercially available monomers – laurolactam for PA12 and caprolactam for PA6. This enables the possibility of changing the properties such as the transparency of the polyamides PA6 and PA12, thus extending their application profile.

Currently, the Fraunhofer scientists are working on further improvements of the monomer synthesis which is essential for an economically viable polyamide. Furthermore, they are investigating the properties of the polymers in detail to identify potential applications and implement commercial use of the biopolyamides together with industrial partners.

Source: Fraunhofer Institute for IGB

Coca-Cola: First Ever Plastic Bottle Based on Recycled Marine Waste

Coca-Cola has unveiled the first ever sample bottle made using recovered and recycled marine plastics, demonstrating that, one day, even ocean debris could be used in recycled packaging for food or drinks. This sample is the first ever plastic bottle made using marine litter that has been successfully recycled and reused in food and drink packaging.

About 300 sample bottles have been produced using 25% recycled marine plastic, retrieved from the Mediterranean Sea and beaches. A small step for now, but the technology behind it has big potential.

Revolutionary Enhanced Recycling Technologies

The marine plastic bottle has been developed to show the transformational potential of revolutionary ‘enhanced recycling’ technologies, which can recycle previously used plastics of any quality back to the high-quality needed for food or drinks packaging.

Enhanced recycling technologies use innovative processes that break down the components of plastic and strip out impurities in lower-grade recyclables so they can be rebuilt as good as new. This means that lower-grade plastics that were often destined for incineration or landfill can now be given a new life. It also means more materials are available to make recycled content, reducing the amount of virgin PET needed from fossil fuels, and resulting in a lower carbon footprint.

The sample bottle is the result of a partnership between Ioniqa Technologies, Indorama Ventures, Mares Circulares (Circular Seas) and The Coca-Cola Company. Although enhanced recycling is still in its infancy, the partners produced the sample marine plastic bottle as a proof of concept for what the technology may achieve in time.

In the immediate term, enhanced recycling will be introduced at commercial scale using waste streams from existing recyclers, including previously unrecyclable plastics and lower-quality recyclables. From 2020, Coca-Cola plans to roll out this enhanced recycled content in some of its bottles.

Working Towards Zero Waste

Bruno van Gompel, Technical and Supply Chain Director, Coca-Cola Western Europe, says the potential for the technology is huge: “Enhanced recycling technologies are enormously exciting, not just for us but for industry and society at large. They accelerate the prospect of a closed-loop economy for plastic, which is why we are investing behind them. As these begin to scale, we will see all kinds of used plastics returned, as good as new, not just once but again and again, diverting waste streams from incineration and landfill.”

Tonnis Hooghoudt, CEO of Ioniqa Technologies, the Dutch company that developed the proprietary enhanced recycling technology, says: “The impact of enhanced recycling will be felt on a global scale: by working with Coca-Cola and Indorama to produce this bottle, we aim to show what this technology can deliver. Our new plant is now operational and we are bringing this technology to scale. In doing so, we aim to eliminate the concept of single use plastic and plastic waste altogether.”

Source: Coca-Cola

New Project to Produce Biodegradable Plastics from Weeds

Max Planck Institute for Chemical Energy Conversion (MPI CEC) launched a joint sustainability project with Addis Ababa University in Ethiopia to produce sustainable chemical products from Vernonia galamensis.

MPI Director Prof. Walter Leitner and his department at MPI CEC focuses on "green chemistry". 

Their research is concerned with the manufacture of chemical products without using fossil resources.

Green Collaboration

Leitner, an honorary member of the Chemical Society of Ethiopia, initiated the collaboration together with Prof. Yonas Chebude, Head of the Faculty of Chemistry in Addis Ababa. 

Prof. Chebude and his team are conducting intensive research in Ethiopia on the conversion of biomass into chemically usable products. 

Vernonia galamensis – Raw material for Epoxidized Oil

They are currently focused on the plant Vernonia galamensis - normally thought of as a "weed". The plant produces 40% epoxidized oil which is promising for industrial production. The molecules contained therein are naturally reactive and can therefore be used much more easily as an industrial raw material than other vegetable oils. 

Their research group is now trying to produce "green" chemical products - such as biodegradable plastics or adhesives - from the oil. This requires catalysts that will be developed jointly as part of this project. 

There is currently no commercial cultivation of the plant, but there is already a high demand for the oil. 

Prof. Yonas Chebude said that if sustainable products can be produced from the weeds, it would be a progress in the field of green chemistry but also a lucrative export product for Ethiopia.

The project is supported by a private donation from Mrs. E. Junesch and will initially run for one year. 

Prof. Walter Leitner said that sustainable products made from Vernonia galamensis would greatly benefit Ethiopia as the research and production would take place locally.

Source: MPI CEC

New Method to Convert Waste Fat into PHA Using Oxy-gas Bacteria

Researchers at TU Berlin are researching to replace plastics from petroleum - with the help of bacteria.

Waste Fats: Raw Material for Alternative PHA

A timid approach to dealing with plastic plague is PHA (polyhydroxyalkanoates). They are biopolymers and are used widely as they are like plastic from fossil fuels.

"Half of the two million tons of bioplastics that are currently produced worldwide per year are not biodegradable and the other half are sometimes difficult to," says Riedel. Therefore, a need arises for alternative PHA based on other raw materials.

The raw material can be obtained from many substances like corn, sugar, glycerine or palm oil. Sebastian L. Riedel and Stefan Junne, however, had a basic product that does not pollute the climate and is not food or feed such as corn as such a source material is considered problematic.

In the search for an alternative, they decided waste fats among other things, which are incurred, inter alia, in agriculture (animal carcasses), in catering or in the processing of food waste. Trash and leftovers for others but valuable raw materials for the scientists.

Oxy-gas Bacteria for Converting Waste into PHA

The accomplishable bacteria called Ralstonia eutropha or Cupriavidus necator, also known as oxyhydrogen bacteria. We let them 'piss us off' for us, " laughs Riedel.

The Process:

• The bacteria are kept in a mineral salt solution, fed with nitrogen, phosphorus, oxygen and carbon
• The carbon is added in the form of waste fats
• Then the bacteria are left to grow
• After a certain time, the nitrogen is removed from the bacterial culture
• They respond to this deficiency by investing the excess carbon in the waste fat as an energy reserve in their cells and converting it into PHA
• Then the PHA produced in the cells is extracted with the help of solvents, some of which can be recovered after the process
• If nitrogen is given back after a certain period, the bacteria would first use the intracellularly stored PHA as an energy source, hence it should not be done

The researchers are working on alternative refurbishment methods that will make the process more cost-effective and sustainable in the long term.

Renouncement of Research With Palm Oil

Dr.-Ing. Incidentally, Sebastian L. Riedel began his research on palm oil with PHA ten years ago in the United States at the Massachusetts Institute of Technology (MIT). "This is a super uncomplicated starting material for the production of the substance," says Riedel.

But the palm oil plantations are tackling the rainforest. When he came to the TU Berlin in 2012, he discontinued his research on palm oil. "Replacement found for plastic, cutting down rainforest - that cannot be the result of research," Riedel explains his decision.

Since 2017, Riedel has been expanding its PHA research with biogenic residues at the Department of Bioprocess Engineering, which is committed to the development of sustainable bioprocesses.

Source: TU Berlin

New Biopolymer-based Heart Valve Implanted in First Patient

Caltech researchers have helped to design a new generation of heart valves that are longer-lasting, cost less to manufacture, and are more biocompatible than options that are currently available to patients. As part of an FDA trial, one of the new valves was implanted into a human for the first time in late July.

New Tria Valve for Aortic Valve Disease 

The new Tria heart valve was created by Foldax® Inc., a Caltech startup cofounded by Mory Gharib, the Hans W. Liepmann Professor of Aeronautics and Bioinspired Engineering in the Division of Engineering and Applied Science. Gharib and his team worked closely with Foldax lead designer Jason Beith in designing the new valve. It was implanted in a patient with aortic valve disease at Beaumont Hospital in Royal Oak, Michigan, as part of an FDA Early Feasibility Study (EFS).

Newly Developed Biopolymer Material for Durability

The Tria valve uses a newly developed biopolymer material coupled with a bioinspired shape to create a valve capable of lasting decades without calcification, risk of clotting, or damage to red blood cells. 

“In testing, one valve already has lasted for 600 million cycles—the equivalent of around 15 years—without signs of significant wear and tear”, Gharib says. 

"It's a powerful combination of the bioinspired design and advanced engineering that we have at Caltech," Gharib says. "This is among my proudest moments. Creating something with the potential to save and improve lives is one of the reasons I became an engineer."

Next Iteration: Inserting Minimally Invasive Catheter

The next iteration of the valve, which Gharib has already designed in prototype with Foldax, will allow it to be inserted via a minimally invasive catheter. It uses a polymer that is bonded to a metal frame in a process refined by Gharib and his team at Caltech.

The unique polymer that was key to the valve function was developed in partnership with Australia’s national science agency, the Commonwealth Scientific and Industrial Research Organization (CSIRO). Robert Grubbs, the Victor and Elizabeth Atkins Professor of Chemistry who consulted on the polymer synthesis and characterization, is a member of Foldax's scientific advisory board.

Aortic Valve Disease

A condition where the valve between the main pumping chamber of the heart and the body's main artery stops functioning properly—can either be congenital, age-related, or the result of other diseases. 

The heart valve that the Tria is intended to replace has three flaps, or leaflets, connected by flexible tissue. As the heart beats and pumps blood through the valve, the flexible tissue bends outward, opening the valve. In between the beats, the flexible tissue bends back in, closing the valve and preventing blood from flowing backward. When the leaflets become diseased, they stiffen and impede blood flow.

Individuals affected by the disease often require open heart surgery to replace the malfunctioning valve, for which they have had two expensive options: 

A mechanical valve: They are crafted from a synthetic material such as pyrolytic carbon, are the more durable option, but require patients to go on lifetime blood thinners to prevent blood clotting and can cause damage to red blood cells.

A tissue valve: These are painstakingly hand-stitched from animal heart tissue, present less risk of causing clots and cellular damage but are less durable than mechanical valves due to calcification and general wear and tear.

Latest Example of Entrepreneurial Innovation

This heart valve is just the latest example of entrepreneurial innovation by Gharib and Grubbs. In 2017, Gharib unveiled a smartphone app that measures left ventricle ejection fraction (LVEF), a major indicator of heart health, through Caltech startup Avicena. Grubbs, winner of the 2005 Nobel Prize in Chemistry, founded the startup Materia in 1998 to market catalysts. Materia has since partnered with Cargill to produce biofuels.

"Our researchers, with all of their ingenuity, serve the greater good by inventing, but also commercializing, technologies that make a significant difference in people's lives," says Fred Farina, chief innovation and corporate partnerships officer at the Caltech Office of Technology Transfer and Corporate Partnerships. "Real-world impact is an important measure of a university's success, and Caltech is scoring high on this aspect. I am certain it will continue to do so for many years to come."

Source: Caltech