CO2 as a Monomer for Polymer Synthesis

The low cost and low toxicity of CO2 make it an attractive industrial chemical reagent, and the utility of CO2 is dramatically illustrated by the fact that millions of tons of CO2 are consumed per year in the industrial production of urea. Other methods for using CO2 as a practical carbon feedstock are being aggressively investigated, and one of the most intensely studied processes involves the use of CO2 in the synthesis of polymers, especially polycarbonates and polyurethanes. The current industrial synthesis of those materials is primarily based on the condensation of highly toxic phosgene and aromatic or aliphatic diols. Because CO2 would provide a less expensive, less toxic alternative to phosgene, considerable effort has gone into developing those CO2-based synthesis .

Researchers from Bayer MaterialScience and Bayer Technology Services are working together with RWE Power AG and academic partner RWTH Aachen University on the sustainable use of carbon dioxide (CO2). At the heart of what has been called the ‘Dream Production’ project, sits the construction and commissioning of a pilot plant at Chempark Leverkusen. This is to be the location for the kilogram-scale production of polyether polycarbonate polyols (PPPs) that will be processed into polyurethanes and will involve the chemical bonding of CO2, which will be an integral raw material in this sustainable process. The key process for this is ‘catalysis’.

While catalysis is currently used in the manufacture of more than 85 percent of all chemical products, the low-energy density of CO2 has hindered the application of this technology in any attempt to put CO2 to practical use.

But in recent laboratory tests, ‘dream reactions’ have been achieved; i.e. reactions created in a laboratory but the industrial applications of which have yet to be proven; resulting in the process being described as a ‘dream’, for the time being.

For the first time, these promising results will be transferred from the laboratory to a larger scale in the ‘Dream Production’ project. During the next three years, the German Federal Ministry of Education and Research (BMBF) will invest a total of more than €4.5 million in the initiative, the project supervision of which is the German Aerospace Center (DLR).

Polyether polycarbonate polyols (PPP) produced using catalysis are extremely attractive materials. As well as the incorporating CO2 in the process, there are also further interesting possibilities involving their use in polyurethane chemistry. “Using the waste product CO2 to manufacture versatile materials is an amazing achievement made possible by catalysis – and one which both we and our project partners are very proud of,” said Patrick Thomas, CEO of Bayer MaterialScience AG. “What’s more, as an ultra-efficient organic insulating material, polyurethanes save around 80-times more energy during their service life than is required for their production. This ensures that PPPs have a doubly positive effect on climate protection.”

As well as being used for building insulation, lightweight polyurethane components also help to reduce weight in the automotive industry, for example, resulting in significant energy savings. However, polyurethanes are also part of everyday life when used as a material for manufacturing high-quality mattresses and upholstered furniture.

‘Dream Production’ is based on a forerunner project ‘Dream Reactions’, which was initiated by Bayer Technology Services and also funded by the BMBF. “As part of this project, we dealt with fundamental questions focusing on harnessing CO2 by using newly developed catalysts. We have achieved promising results that form the basis for industrial implementation in the Dream Production project,” explained Dr. Dirk Van Meirvenne, MD of Bayer Technology Services GmbH.

“The rewarding collaboration with Bayer MaterialScience and Bayer Technology Services as part of the CAT Catalytic Center, laid the foundations for this consortium. Unifying the entire value chain from the source to the product in one single project is unique in CO2 usage. This offers enormous opportunities but also requires open and intensive communication, an aspect that was a great success in the project preparation phase,” said Prof. Walter Leitner, Executive Director of the Institute of Technical and Macromolecular Chemistry (ITMC) at RWTH Aachen University.

Using CO2 as a raw material for manufacturing polymers helps cut consumption of conventional raw materials and therefore fossil fuels. This strategy also shows future generations how to make sustainable use of natural resources.

The CO2 used for the project will come from RWE Power’s lignite-fired power plant at Niederaußem. This is where the electricity generator operates a CO2 scrubbing system at its coal innovation centre, by which the carbon dioxide is captured from the flue gas. For the Dream Productions project, the CO2 scrubber will be equipped with an additional liquefaction system so that the carbon dioxide can be transported to Leverkusen. The CO2 liquefaction system will be designed and operated with flexibility to meet various CO2 pressures and purities on a scale ranging from kilograms up to tonnes.

About Bayer MaterialScience

Bayer MaterialScience’s 2009 sales was €7.5 billion. Its business activities are focused on the manufacture of high-tech polymer materials and the development of innovative solutions for products used in many areas of daily life. The main segments served are the automotive, electrical and electronics, construction and the sports and leisure industries. At the end of 2009, Bayer MaterialScience had 30 production sites and employed approximately 14,300 people around the globe. Bayer MaterialScience is a Bayer Group company.

About RWE Power

RWE Power is an electricity producer in Germany. Over 15,000 employees work in the opencast mines and power plants, processing facilities and research projects, training centers and administration offices. With a power plant capacity of just over 33,000MW, the company contributes to RWE’s broad-based energy mix of lignite, hard coal, nuclear power, gas and renewable energy. RWE Power invests billions in the construction of new, low-carbon power plants and in the development of even more efficient, environmentally benign technologies for power generation in the future.

Novomer introduces biodegradable polymer

The activation and application of CO2 as a carbon source are rather limited. For example, in the organic materials area only urea, salicylic acid, and some cyclic carbonates can be viably produced from CO2. However, CO2 can be copolymerized with heterocycles (epoxides, aziridines, episulfides) to yield novel alternating copolymers.

Of these, polycarbonates represent a very promising class of material; they are thermoplastic and can be produced in reasonable efficiency from C02 and epoxies. Initial studies have also indicated that aliphatic polycarbonates can be recycled via hydrolysis reactions and in some cases biodegraded.

Way back in 1969, researchers found a way to make biodegradable plastics called aliphatic polycarbonate from CO2. Zinc catalyzed sequential copolymerization of CO2 and epoxide was reported as a route to producing polycarbonates. This discovery illuminated for the first time the potential of CO2 as a feedstock for large-scale polycarbonate systems. Alternating copolymerization of CO2 and propylene oxide has also been found to yield polypropylene carbonate (PPC), a thermoplastics material that can be processed by molding or extrusion.

Affordable, biodegradable plastics made from CO2 are moving closer to market. Novomer (Ithaca, NY, USA), a Cornell University spin-off is exploring a different catalyst technology to produce aliphatic polycarbonates. Novomer claims to be able to convert CO2 into everyday plastics such as packaging, cups, and forks. Currently, the plastic is being made on a pilot scale, and Novomer declines to give details of its commercial-scale manufacturing plants.


Novomer and DSM to Develop First Sustainable Carbon Dioxide-Based Resin for Coatings

Novomer, Inc.
a sustainable materials company pioneering a family of high-performance plastics, polymers and other chemicals from renewable feedstocks such as carbon dioxide (CO2) and Royal DSM N.V., the global Life Sciences and Materials Sciences company, have announced that they have signed a joint development agreement to develop revolutionary polyols for coating and ink resins produced using CO2 as a raw material.

This development agreement follows an investment by DSM Venturing in Novomer in 2007. This joint development project will benefit from the broad variety of technologies and market access of DSM, in combination with the unique, efficient CO2 polymerization technology of Novomer.

The chemistry and process technology for producing polyols from CO2 and propylene oxide (PO) will be developed by Novomer, while DSM will convert the polyols into resins and formulate them for target applications such as coatings, adhesives and graphic arts. Potential applications include food and beverage can coatings and linings, coil coating, and automotive and industrial finishes. The first application results have been encouraging and suggest that this project might lead to completely new and unprecedented properties in coatings.

As Novomer’s materials comprise up to 50% CO2 by weight, they deliver significant environmental benefits including:
•Require up to 50% less petroleum to produce than conventional polyols;
•Sequester CO2 in the manufacturing
•Enable the replacement of conventional polyol resins (as Novomer’s manufacturing process is highly efficient) in a number of coating applications including UV curable coatings, heat curable coatings and waterborne dispersions
Conventional polycarbonate polyols are widely known because of their superior performance and environmental resistance, but also for questions around the safety of extractable chemicals. Of particular concern is the use of BPA containing materials for food and beverage can linings. With anticipated comparable performance and cost attributes, greater environmental friendliness, and containing no BPA, Novomer’s polyols can potentially be used in a much broader array of end products.

Rob van Leen, Chief Innovation Officer of DSM, said: “DSM and Novomer are looking to develop the first polymer to enter the main stream of the coating industry for more than a decade. This exciting development can lead to a breakthrough that could change the coating industry. While addressing cost-issues, these innovative coating resins also address environmental and performance issues. It therefore fits perfectly within DSM’s People, Planet and Profit approach.”

Peter Shepard, Vice President of Business Development of Novomer adds: “We are very enthusiastic about our relationship with DSM as they bring a wealth of skills and industry knowledge to help drive the commercialization of our technology in the coatings industry. In addition, this product development relationship with DSM leverages our ongoing technical development work that has been supported by NYSERDA (New York State Energy Research and Development Authority) and the National Science Foundation SBIR program.

About DSM NeoResins+
DSM NeoResins+ is a leading, committed, global supplier of innovative specialty resins for the coatings and graphic arts industries. The waterborne product lines include acrylics, urethanes, alkyds and polyesters. The solvent borne product lines include polyesters, acrylic, alkyds, urethane and amino resins and acrylic beads.
DSM NeoResins+ has 1,250 employees and operates seven manufacturing sites spread over Europe, US and China. Being focused on customer needs, it has five Application and Research & Technology Centers supported by a Customer Service Center in each of the three continents. DSM NeoResins+ is headquartered in Waalwijk (Netherlands).

DSM – the Life Sciences and Materials Sciences Company
Royal DSM N.V. creates innovative products and services in Life Sciences and Materials Sciences that contribute to the quality of life. DSM’s products and services are used globally in a wide range of markets and applications, supporting a healthier, more sustainable and more enjoyable way of life. End markets include human and animal nutrition and health, personal care, pharmaceuticals, automotive, coatings and paint, electrical and electronics, life protection and housing. DSM has annual net sales of EUR 9.3 billion and employs some 23,500 people worldwide. The company is headquartered in the Netherlands, with locations on five continents. DSM is listed on Euronext Amsterdam. More information:

See also:

Novomer introduces biodegradable polymer
Chinese project

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