Since high-performance materials follow the path taken by some commercial resins, agriculture may replace drilling because suppliers rely more on plants than oil or natural gas as raw materials. #Sustainability

Arkema's 100% bio-based Rilsan nylon 11 won the "green" award for diesel fuel lines and camera lens caps.

DSM's EcoPaXX nylon 410 crankshaft cover for next-generation Volkswagen diesel engines is 40% lighter than existing nylon 46 and 66.

DuPont's bio-based Hytrel RS copolyester has a PBT hard segment and a renewable PTMEG soft segment. It is used to make the Knoll Flex Back Next Generation chair. It will bend as you change position to respond to your movements.

The 2012 Toyota Prius Alpha used DuPont Sorona's renewable source PTT polyester in the air-conditioning shutter blades. PTT was chosen because of its heat resistance, durability and reduced environmental footprint.

In the past five to ten years, commercial resins such as polyolefins and PET have been at the forefront of bio-based and recycled content news, but some engineering thermoplastics have been catching up. To ensure that this sustainable plastic is widely adopted, suppliers have been working to make them comparable to traditional resins in terms of performance and cost-effectiveness.

Driven by markets such as packaging, automobiles, electronic products, consumer goods, and medical equipment, engineering resin suppliers are increasingly using vegetable oil, sugar or starch to develop bio-sourced raw materials to synthesize new orders for some of their key materials. The focus of several companies is to develop sugar sources from crop waste or other renewable chemicals from non-food biomass. Most commercial activities are concentrated on nylon and polyester, but some are aimed at high-end TPE and TPU.

The presentation of Innoplast Solutions, Inc. at the "Reinventing Plastics Through Renewable Chemicals" conference held in Miami in January this year demonstrated these trends. Speakers include leaders in the field, such as DuPont, Wilmington, Arkema, King of Prussia, Pa., DSM Engineering Plastics ) (Birmingham, Michigan) and Cathay Industrial Biotech in China (Powell, Ohio, USA) discussed its latest activities and future goals.

Other companies active in the development of bio-based engineering resins include BASF, Florham Park, NJ, Evonik, Parsippany, Solvay Specialty Polymers, Alpharetta, Ga., Invista, Wichita, Kan. and Lanxess, Pittsburgh. Others are Lubrizol Engineered Polymers, Cleveland, Elevance Renewable Sciences, Woodbridge, Illinois, and Rennovia, Santa Clara, California.

Most of these developments require partnerships or acquisitions with agricultural companies. An early example is DuPont, which divested ConocoPhillips and acquired Pioneer Seeds in 1999 to become a world leader in agribusiness. The company reported that the division accounted for 32% of 2013 sales, of which high-performance chemicals accounted for 19%. (The latter will be split this year.)

Nylon: The oldest 100% bio-based engineering thermoplastic, both old and new, is nylon 11. Exclusively manufactured by Arkema and sold under the Rilsan brand, this 40-year-old material is entirely based on castor oil and has long been used in truck air brakes and other applications. In recent years, it has gained recognition in diesel fuel lines and camera lens caps.

Nylon 610 is another "green" resin (60-64% from castor oil), with a long history of more than 50 years, and has entered the fuel tank and fuel line of the car radiator. It is available from a number of suppliers, including Arkema, DuPont, BASF, Solvay, and Ems Chemie (located in the US office in Sumter, South Carolina).

In 2009, Arkema launched the first transparent bio-based nylon Rilsan Clear G830, which is a highly transparent amorphous nylon with a bio-based content of 54%. It has been used in applications ranging from sports or designer optical frames to breathing masks and hearing aids. Its weight is 10-20% lighter than ABS, PC, PMMA or nylon 6. It is closely followed by Rilsan HT; it is a high-temperature polyphthalamide (PPA) extruded resin with the unusual flexibility of PPA. It has achieved success in the metal-to-plastic conversion of engine compartment ducts. 

Bio-based Rilsan T nylon 1010 was launched in 2013 and is a unique long-chain nylon. In addition to the chemical resistance and mechanical properties of long-chain nylon, it is said to have excellent rigidity, thermal stability, fuel impermeability and processability. This 100% bio-based material further expands Arkema’s product range and was promoted by the company’s 2012 acquisition of the Chinese company Casda, a global leader in sebacic acid derived from castor oil; and the production of Hiprolon 610, 612 , 1010, 102 Hipro Polymers. Arkema also bought shares in Ihsedu Agrochem, India, which produces castor oil.

There are now several nylon suppliers whose material monomers are partly or completely derived from castor oil, with a minimum bio-based content of 20%. One thing these new nylons have in common is nylon 10, which is 100% castor-based like nylon 11. They include: BASF (Ultramid Balance nylon 610); DSM (EcoPaXX nylon 410; DuPont (Zytel RS nylon 610 and 1010), Evonik (Vestamid Terra nylon 610, 1010 and 1012); Solvay Engineering Polymers (Technyl eXten nylon 610) Acquisition of Rhodia); and Ems Green Chemie, the production line includes nylon 610 and 1010 and PPA.

Several companies are purchasing current and developing bio-based materials from other renewable plant resources. For example, in DuPont, this includes sugar cane, corn, soybeans, and wheat. In 2013, the company revealed that it was carrying out a major R&D activity aimed at replacing more than half of the existing plastic product portfolio with bio-based versions as direct substitutes within a 15-year time span. The company also aims to make these renewable polymers cheaper and/or higher performance than petroleum-based polymers to further increase the interest of OEM end users.

Michael Saltzberg, Business Director of DuPont Biomaterials, gave just one example: "We are the first company to introduce nylon 610 into radiator tail box applications (Toyota). But the main driving factor for its use is not its bio-based content, but It offers a cost/performance balance compared to nylon 12." He pointed out that the shortage of nylon 12 in 2012-13 led to a substantial increase in nylon 610 and 1010. In addition to bio-based components, these two materials have better properties than nylon 12. The thermal performance.

In the automotive field, Jeff Sternberg, DuPont's global automotive technology director, pointed out that the main focus is to reduce emissions by improving fuel economy. Although currently renewable source materials and/or recycled materials are not so important in themselves, market interest is definitely increasing. "DuPont is developing polymers based on bio-based raw materials that will provide improvements for under-hood applications such as fuel tanks, fuel tanks, engines and chassis components," he said.

BASF has introduced Ultramid nylon for flexible packaging films. The company replaces up to 100% of fossil resources with certified biomass. The third-party certification confirms to the customer that BASF has used the percentage of renewable raw materials specified by the customer. Ultramid nylon produced by this so-called mass balance method is the same as traditional materials in terms of formulation and quality, but has lower greenhouse gas emissions.

DSM's EcoPaXX nylon 410 (70% bio-based content) demonstrated its strength in fuel vapor separators produced for Ferrari and Maserati. The halogen-free flame retardant grade Q-KGS6 combines flame retardancy (UL 94V-0 rating at 0.7 mm) with the high chemical resistance required for this application.

This material is also used in the production of multifunctional crankshaft covers for next-generation Volkswagen diesel engines. The cover plate replaces nylon 46 and 66. Compared with aluminum flanges of similar geometry, the weight is reduced by 40% and the cost is reduced by 25%. The material is also used in fuel line connectors to replace existing grades of glass fiber reinforced PPA or nylon 12.

The newer EcoPaXX grade can replace the current insulating profiles mainly made of nylon 66 and assembled into aluminum frames. Its high melting point of 250 C allows it to pass through a powder coating process in a fully assembled aluminum frame. It also has much lower hygroscopicity than nylon 66. Other new brands are making their debut in high-performance sports shoes, spectacle frames and electronic wire-to-board connectors.

At the same time, DSM's German development partner MF-Folien produced the first EcoPaxx films. They have a higher moisture barrier than nylon 6 film and equivalent oxygen barrier properties. Their goals are applications in flexible food packaging, construction, medical, aviation and shipping.

Since the launch of the 3000 and 2000 series (for mobile electronics) at the 2013 K show, Solvay Specialty Polymers has been expanding its improved bio-based Kalix HPPA (high-performance polyamide) resin series. The 3000 series is based on a completely new molecule and claims to be the first bio-based amorphous PPA. It contains 16% sebacic acid from renewable sources and 50% glass fiber. The semi-crystalline 2000 series contains 27% renewable ingredients and is based on nylon 610, but has better impact and flow properties.

Solvay has now added the halogen-free flame retardant grades of Kalix 2000, including Kalix 2930 HFFR and 2945 HFFR, which are candidates for notebook computer applications. The company has also developed opaque black laser welding grades based on Kalix 2000 and 3000 as an option for structural parts that require laser welding to improve water resistance.

In addition, the company has made progress in both series in the field of medical equipment. These materials show significantly better chemical resistance than PC or PC/ABS in the frame and housing of mobile medical equipment.

Challenge nylon 66 Pursue the "Holy Grail" of nylon 66. Together with nylon 6, it is the nylon with the largest output and has always been the focus of suppliers' attention. Cathay Industrial Biotech has been using renewable resources such as sugar, palm oil and castor oil to produce bio-based nylon. The company launched a new nylon series produced with a new proprietary technology that can produce 1,5-pentanediamine monomer from sugarcane, making it 100% renewable. According to reports, the performance of this new type of 5 carbodiamine is comparable to that of 6 carbodiamine-1,6-hexamethylene diamine (HMDA) currently used in many nylons, and it also provides new features in special applications. characteristic. The Terryl series includes nylon 56, 510, 512, 514 and 612.

Cathay Pacific President and co-founder Paul Caswell demonstrated in the Innoplast conference that the properties of nylon 56 are very similar to nylon 66, but the sustainable content is 47%. Test products include cable ties (pure nylon 56); heated insect repellent shells (pure nylon 56); and electrical component shells (30% glass filled nylon 56). He pointed out that Cathay Pacific’s first factory will use corn sugar; the company is also studying non-food, biomass-based sugar extracted from agricultural waste, and plans to gradually convert it as the technology develops.

Rennovia has produced the development of its Rennlon 100% bio-based nylon 66 and is working with partners to make this product enter the commercial market for the first time in the world. It is made from Rennovia's renewable monomers, adipic acid (AA) and hexamethylene diamine (HMD). The company expects that the production cost of bio-based AA and HMD will be 20-25% lower than the petroleum-based version. Rennovia has received a US$25 million equity investment from Archer Daniels Midland.

Invista collaborated with LanzaTech (US office in Skokie, Illinois) to develop bio-based butadiene as a raw material for the manufacture of adiponitrile (ADN), an intermediate for nylon 66. LanzaTech initially converts carbon monoxide (CO) to 2,3-butanediol and then uses gas fermentation to convert it to 1,2-butadiene. The two companies plan to directly use a single-step process to produce CO-based butadiene through gas fermentation by 2016.

TPES and specialty copolymers In 2007, DuPont introduced Hytrel RS TPE and Sorona EP PTT polyester, both of which are made from propylene glycol (PDO) derived from fermented corn starch. Hytrel RS copolyetherester TPE has PBT hard segment and renewable PTMEG soft segment. The renewable content varies according to the required hardness. These materials have been used in automotive and industrial hoses and pipes, constant velocity joint (CVJ) shields, airbag doors, energy dampers, air ducts, and coil wires. They are also used in furniture, such as the hanging webbing of the new Knoll "Generation Chair". The softer version may be used for mobile phone casings and wire insulation.

Sorona EP PTT is a unique thermoplastic polyester with a bio-PDO content of 37%. Its targets are electrical and electronic components, electrical parts, power tool applications, furniture, medical applications, and automotive components. According to reports, the material has been used to make medical biopsy punches.

Its car debut was in the 2012 Toyota Hybrid Prius Alpha, and it was selected as the ventilating shutter blade due to its heat resistance and durability. In addition to lower warpage and Class A surface appearance, the 45% glass-filled Sorona part eliminates the additional paint step required in the past to fill PBT with 45% glass. DuPont is looking for other similar applications.

In 2010, Arkema launched its first engineered TPE made from renewable resources. Pebax Rnew Polyether Block Amide (PEBA) combines the rigid block of nylon 11 with the soft hydrophobic polyether block to produce a resin with a biological content of 20-95%. These TPEs have been used in sports shoes and other sports equipment, as well as in blends with other resins.

In her Innoplast presentation "Bio-based high-performance polyamides: consumer market solutions", Arkema consumer market business development engineer Min Zheng concluded that by combining Rilsan nylon and Pebax Rnew, manufacturers can now design 100% bio-based consumer product resins, from mobile phone cases and sports shoes to electrical appliances, hygiene and beauty products, films and packaging.

The two companies have made significant progress in bio-based TPU. At NPE2015, Lubrizol launched a new TPU series made from 30-80% renewable source materials. Its hardness ranges from 82 Shore A to 55 D and is suitable for sports, footwear, electronics and automotive applications.

Elevance Renewable Sciences recently announced that it has developed a TPU based on a polyester polyol building block derived from a renewable plant source-Elevance Inherent C18 Diacid. The result is a new semi-crystalline TPU with potential in applications such as automotive brake linings and sports equipment.

At the same time, Germany's LANXESS uses 20 metric tons of bio-based BDO (1,4-butanediol) to produce Pocan PBT, which is made using a process developed by San Diego Genomatica. This process converts sugar into BDO in a patented direct fermentation process. According to LANXESS, bio-based PBT compounds are a direct substitute for mature PBT automotive or electrical/electronic applications.

BASF recently announced that it is now providing selected partners with bio-based polytetrahydrofuran 1000 as an intermediate for testing various polymer synthesis applications for the first time.

PolyTHF1000 is a polymer made from linear diols, and its main chain is repeating tetramethylene units connected by ether bonds. It can be used as a building block for soft segment elastomers (such as TPU, copolyetherester and copolyetheramide).

Polytetrahydrofuran is derived from 1,4-butanediol (BDO). BASF is now using Genomatica's patented one-step sugar fermentation process to produce BDO. Applications range from ski boots and shoe soles to car dashboard skins, hoses, films and cable sheaths.

PET has strong hygroscopicity, high moisture sensitivity, and is one of the most difficult drying challenges. The following are the basic principles for preparing for rigid packaging applications

This is a quick guide to solving four annoying problems in handling PET bottles.

The so-called "marine plastic" is a global issue, but many companies throughout the supply chain have invested the necessary time, money, and research and development work to capture and transform this material into a sustainable business. But the demand must follow.

© 2021 Gardner Business Media, Inc. Privacy Policy [Login]