Plant based nylon

Excerpt: POLYAMIDES are important industrial polymers. Currently, they are produced exclusively from petrochemical monomers. About six billion pounds of Nylon 6,6 is made every year

President, Colorant Ltd.

3225, Phase IV, G.I.D.C. Vatva, Ahmedabad - 382445, Gujrat - INDIA.

POLYAMIDES are important industrial polymers. Currently, they are produced exclusively from petrochemical monomers. About six billion pounds of Nylon 6,6 is made every year. It is used in products like carpets, tire cord, ropes, apparel, hoses, blankets, zip ties and even guitars.

How toxic is Nylon 6,6 for long-term exposure to humans? What about to other species? Six billion pounds a year of a material containing chemicals derived from petroleum sounds like a great deal of plastic resin that doesn't appear to be very environmentally or human friendly.

Another question: does the bio-based polymer generate less toxic gases when it burns? Nylon 6,6 is used in automobiles, so would it reduce toxic gases from fires to use a bio-based version?

Some sources say nylon could be harmful, such as the Environmental Health Association of Nova Scotia, which lists it as a harmful ingredient for babies on their website. Others might say it doesn't seem to have caused much harm so far, and it is nearly everywhere so it probably isn't toxic.

Still, if it can be replaced with a cheaper version and made from renewable sources, it sounds like the kind of change that would be sensible. Though it may not be very harmful at all, one less source of petroleum-based chemicals in our environment couldn't hurt.

Polyamide (PA), commonly known as nylon, is a polymer with a myriad of pharmaceutical and industrial applications. Chemically, the polymer backbone is composed of repetitive units of diamines and dicarboxylic acids that contain different numbers of carbon atoms, imparting a variety of material properties. Commercialized in the 1940s, polyamides have entered the market place on a large scale for the manufacturing of fibers for clothing or thermoplastics for carpets, cogs, car parts, tire reinforcements, and other products (Carole et al., 2004). Currently, the global market requires 6.6 million tons per annum, making polyamides one of the most important industrial polymers. Its good biocompatibility has further led to its implementation in medical applications, such as providing a scaffold for tissue cultures (Yoo et al., 2011), foil for orbital implants (Park et al., 2008), and bone support in arthroplasty (Edwards et al., 2011). Novel developments extend the application range of polyamides to diagnostics (Cox, 2001) and cellular control devices in molecular medicine (Schmitz and Schepers, 2004). Interest in a “green” route for polyamides has arisen due to the inevitable stoichiometric wastes of classical petrochemical production routes, commonly thought to cause global warming and ozone depletion, as well as acid rain and smog (Sato et al., 1998). Compared to other industrial polymers, the production of petrochemical nylon has a markedly severe impact on global climate change, expressed as carbon dioxide equivalents released (Vink et al., 2003). Moreover, it exhibits an exceptionally high requirement for fossil energy, which is particularly unfavorable in the light of the increasing shortage and rising price of fossil resources. Alternative chemical routes, such as the direct oxidation of cyclohexene to the nylon precursor adipic acid (Sato et al., 1998), promise attractive solutions for the reduction of the carbon footprint of polyamides, but these methods still rely on fossil fuels.

The quest to produce a 100% bio-based nylon 6,6 polymer has now come to fruition as Rennovia announced that it has produced and shipped samples of their RENNLON100% bio-based nylon 6,6 polymer, believed to be the first produced worldwide. The bio-based nylon was made from the combination of Rennovia's RENNLON adipic acid and RENNLON hexamethylenediamine (HMD or HMDA). California-based Rennovia has developed chemicals and chemical processes that are bio-renewable to replace petrochemical production.

Production process

Rennovia have produced a 100% bio-based nylon polymer. Compared with petroleum-based adipic acid, which is used in making nylon polymer 6,6, using their bio-based version could reduce climate change emissions by 85%.

The production of 100% bio-based nylon-6,6 further validates Rennovia's unique ability to create technological breakthroughs in the production of bio-based chemicals and materials, with projected significant cost advantages and environmental benefits vs. products produced from petroleum-based feedstocks. The production of a novel bio-nylon, PA5.10 through an integration of biological and chemical approaches involves the following steps. First, systems metabolic engineering of Corynebacterium glutamicum was used to create an effective microbial cell factory for the production of diaminopentane as the polymer building block. In this way, a hyper-producer, with a high diaminopentane yield of 41% in shake flask culture, was generated. Subsequent fed-batch production of C. glutamicum DAP-16 allowed a molar yield of 50%, a productivity of 2.2gL(-1)h(-1), and a final titer of 88gL(-1). The streamlined producer accumulated diaminopentane without generating any by-products. Solvent extraction from alkalized broth and two-step distillation provided highly pure diaminopentane (99.8%), which was then directly accessible for poly-condensation. Chemical polymerization with sebacic acid, a ten-carbon dicarboxylic acid derived from castor plant oil, yielded the bio-nylon, PA5.10. In pure form and reinforced with glass fibers, the novel 100% bio-polyamide achieved an excellent melting temperature and the mechanical strength of the well-established petrochemical polymers, PA6 and PA6.6. It even outperformed the oil-based products in terms of having a 6% lower density. It thus holds high promise for applications in energy-friendly transportation. The demonstration of a novel route for generation of bio-based nylon from renewable sources opens the way to production of sustainable bio-polymers with enhanced material properties and represents a milestone in industrial production.

A polyamide powder from a vegetable source Orgasol green touch has been designed to combine the unique aesthetic properties of nylon powders and the advantages of a natural origin. The 100% plant-based product delivers a velvety & creamy feel, enhanced compaction and visual properties. Orgasol Green Touch is a Polyamide 11, the first polyamide entirely based on a vegetable material. Its manufacturing process has been largely inspired by the key principles of Green Chemistry and is fully handled by Arkema. Renewable feedstock: Orgasol Green touch is based on castor plant (Ricinus Communis), a non-edible and robust crop that does not compete with food crops and grows mostly on poor soils in semi-arid areas.

Rennovia has been able to produce both adipic acid and HMD using glucose for feedstock using its proprietary chemical catalytic process technology. Rennovia produces its bio-adipic acid by aerobic oxidation of glucose to produce glucaric acid, which then undergoes hydrodeoxygenation to produce adipic acid. For Rennovia's bio-HMDA, it is produced by hydrodeoxygenation of glucose to produce a key intermediate, which then undergoes amination to produce bio-HMDA. Production costs for both bio-adipic acid and bio-HMDA are projected to be 20-25% below that of conventional petroleum-based adipic acid and HMDA with a significantly lower per-pound capital cost. The company reported that current global nylon 6,6 market is at 6bn pounds/year worth more than $6bn. Nylon 6,6 is a widely used high-performance engineering resin, used especially in the automotive market for its strength, light weight, and performance at high temperatures. Nylon-6,6 is also used in a wide range of fiber applications, including textiles, carpets, technical fibers and tire-cord.

Rennovia has commercially demonstrated unit for its bio-adipic in 2014 with a fully integrated “mini-plant” designed to allow direct scale-up to the full commercial scale of 135,000 tons/year. Rennovia has anticipated its first commercial-scale bio-adipic acid production in 2018.

Rennovia's strategy is to demonstrate with (an) external partner/s product purity and full equivalence of their bio-based nylon 6,6 product from the integrated mini-plants, with all recycle loops closed. Their product is expected to be fully representative of the commercial-scale product. According to Rennovia, stringent purity specifications will need to be met for both bio-based adipic acid and HMDA to qualify for nylon 6,6 applications.

From past posts on bio-adipic acid, there are several possible routes for the production of this chemical:

  • Direct fermentation to adipic acid

  • Bio-based benzene –> KA Oil –> adipic acid

  • Muconic acid –> adipic acid

  • Bio-based butadiene –> adipic acid

  • Glucaric acid –> adipic acid

Other companies working on bio-adipic acid or looking to expand in this area include Verdezyne, DSM, Amyris (which acquired a bio-based adipic acid technology from the former Draths), Genomatica, BioAmber, and Aemetis.

Verdezyne is developing bio-adipic acid through direct fermentation using a yeast microorganism that can utilize sugar, plant-based oils or alkanes. The company recently announced a collaboration with Malaysia's biotechnology investment agency, the Malaysian Biotechnology Corporation (BiotechCorp) to assess Malaysia as the location for Verdezyne's first biochemical production facility. Verdezyne is expected to use local feedstock such as palm kernel oil and palm fatty acid distillates.

Eco-friendly and sustainable products are in high demand and many manufacturers are searching the philosophers' stone within cutting edge eco-friendly technologies. But Yeti is the first company in the world to introduce a jacket made from eco-friendly plant based nylon, enabling nature lovers to protect nature while enjoying it.

The eco-friendly nylon, called Next To Nature, is based on renewable plant oil instead of scarce fossil oil. The oil is extracted from the Ricinus-plant, a non-food plant that grows mainly on dry wasteland and does not occupy farming land. On the contrary the plant creates new production in dry and destitute areas.

Further more Ricinus is a robust plant that requires significantly less water and thereby less resources. Nylon, based on a renewable source such as plant oil is much more environmentally friendly than traditional nylon made from scarce petroleum products – and the good news is, that being eco-friendly doesn't compromise functionality.

Next to Nature is breathable and feels soft as silk. The fabric is antistatic and PA-coated for water resistance. Next to Nature has been used in the award winning jackets North and Mode and the green sleeping bag Gecco.

World's first plant based nylon from Yeti

Eco-friendly products are more popular than ever, especially among consumers who love nature and the outdoors. Down specialist Yeti has already introduced the world's first jacket made from a new eco-friendly plant based nylon in the spring 2014 collection.

Outdoor enthusiasts explore and adore nature around the world and are naturally interested in protecting it. Therefore eco-friendly and sustainable products are a hit in the outdoor industry and the manufacturers are exploring cutting edge eco-friendly technologies to enable nature lovers to protect nature while enjoying it.

For the spring 2014 collection outdoor specialist Yeti introduces the jacket North made from a new ground breaking plant-based nylon. This is the first garment in the world made from plant based nylon.

Non-water absorbing down filling

But eco-friendliness does not equal compromising on functionality. Quite the contrary. Not only does the plant-based fabric maintain an inherent highly water repellent surface feature. The water repellent outer shell is also combined with another ground-breaking invention, the exclusive Crystal Down Dry filling. The filling is treated with QuixDown Technology by Toray, preventing the down from absorbing water. These two features keep you dry and warm even through heavy showers.

OSAKA – Technology experts at Japanese textile giant Toray say it has combined a new 3D fabric structure with the first plant-based membrane to offer the performance apparel market an ultra-light, soft laminate that is both breathable and water-resistant. The new development will be officially launched at this week's ISPO exhibition in Munich.

Nylon from the sun: Verdezyne opens pilot plant for bio-based adipic acid

In California, Verdezyne has opened its first pilot plant to produce adipic acid, a key component of nylon 6,6. The new facility, located in Carlsbad, California will be used to accelerate the commercialization of Verdezyne's bio-based adipic acid, which is one of two components used to manufacture 'green' nylon 6,6 and thermoplastic polyurethane resins from renewable sources, such as non-food based vegetable oils.

In addition to lower production costs, Verdezyne's method uses non-food, plant-based feedstocks to produce a variety of commercial diacids.

Moreover, Verdezyne's production methods are expected to generate less CO2 and other pollutants as compared with incumbent methods. A variety of products are currently produced worldwide from petroleum-based nylon, including engineered plastics, carpets, clothing and other assorted textiles. Production of these types of products translates to an adipic acid market of more than $6 billion globally.

Verdezyne, Inc., which like Amyris is developing petroleum substitutes from green chemicals, has opened its first pilot plant to make "green" nylon, used for engineered plastics, carpets, clothing and other textiles.

The Carlsbad, California facility will accelerate commercialization of Verdezyne's bio-based adipic acid, a base ingredient for making green nylon 6,6 and thermoplastic polyurethane resins from sources like non-food, plant-based vegetable oils.

"This is the first demonstration of the production of bio-based adipic acid at scale from a non-petroleum source. Our novel yeast platform enables production of adipic acid at a lower cost than current petrochemical manufacturing processes," says Dr. William Radany, president and CEO. The production processes also generate fewer carbon emissions than petroleum production.

Verdezyne says the plant will allow them to demonstrate the scalability of its manufacturing process, validate cost projections and generate sufficient quantities of material for commercial market development.

Ajinomoto partnering with Toray on the development of nylon raw material 1,5 pentanediamine (1,5 PD) using plant-based amino acid lysine via Ajinomoto's fermentation technology.

According to the companies, the amino acid lysine is decarbonated through an enzyme reaction to make the 1,5 PD, and then Toray polymerize the chemical with dicarboxylic acid. An example of nylon that can be made from this process is nylon 5,6 fiber, which Toray said has the same strength and heat resistance as conventional nylon fiber made from petrochemical-based hexamethylenediamine.

The companies have already produced both 1,5 PD and nylon made from the plant-based 1,5 PD in the laboratory. Toray said they plan to further expand their collaboration to include development of production processes and evaluation of use in textile and plastics applications.