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New Developments in Properties for Ethylene Acrylate Polymers 18 Rubber & Plastics News • November 30, 2020 www.rubbernews.com www.rubbernews.com Technical Technical New developments in properties for ethylene acrylate polymers By Patricia Panne, Klaus Kammerer, Serge Bouvier, Ed McBride, Mark Stewart, Steve Oriani and Elias Wang Executive summary DuPont Vamac-brand ethylene acrylic elastomer (AEM) was introduced in 1975 and has been used successfully for many years in the Ethylene acrylate (AEM) polymers transportation sector, where excellent resistance to heat, engine fluids and low temperature flexibility is required. were first introduced to the elastomer With the introduction of the Vamac Ultra grades, a step-change improvement in processability, performance and customer value market more than 40 years ago. They for targeted applications has been achieved. Increasing demands for improved temperature stability led recently to the development are non-crystalline copolymers of eth- of the VMX5000 series of pre-compounds to offer compounds in applications with a 10-15°C higher heat resistance over conventional ylene and methyl acrylate. carbon black-filled AEM compounds. Resistance to engine oils and acids remains excellent, which makes the VMX5000 pre-com- Both monomers add to the high tem- pounds an interesting cost-effective alternative to FKM materials in the temperature range between -35°C and +175°C. perature stability, and the completely sat- For dynamic hose applications, slow-curing polymers (Vamac GXF, Ultra HT and HT-OR) have been introduced. While com- urated polymer chain imparts excellent pounds using the Ultra grades offer better physical properties, they sometimes lead to high extrusion pressure and therefore re- resistance to ozone, oxidation and weath- quire lower hardness compounds (<70 ShA). To offer more compounding flexibility and allow for cost savings, an intermediate ering. The non-polar ethylene contributes viscosity grade called Vamac Ultra XF has been developed that still allows extrusion of 70-75 ShA compounds with superior green to the good low-temperature flexibility strength and physical properties compared to Vamac GXF. while the polar methyl acrylate monomer More stringent safety requirements within the transportation and building sector continue to push for halogen-free, low-toxic- provides the oil and fluid resistance. ity materials. Vamac elastomers are halogen-free polymers and present an interesting option of material when low flammability, toxicity and smoke density combined with heat and fluid resistance are critical. Different starting point formulations have been TECHNICAL NOTEBOOK developed to show the range of HFFR material performance that can be obtained with Vamac. Edited by John Dick are used. For ducts and hoses, often ex- Sealing applications with in- based on three industry-accepted crite- Most of the polymer grades contain a trusion processes are used and slower creased temperature resistance ria: less than 50 percent loss in tensile small amount of acidic cure site monomer curing compounds with improved dy- Typical sealing applications for Va- strength and elongation at break, and for diamine crosslinking. Since the intro- namic properties are needed. mac are cam covers, oil pan gaskets, less than 15-point change in Shore A duction of AEM to the market, the eth- A smaller, but increasingly more im- O-rings and other seals in the air and oil Hardness. ylene-methacrylate ratios have been opti- portant area, is flame retardant applica- circuit of the car covering a temperature Standard Vamac compounds will mized to meet market needs and form the tions. AEM polymers are halogen-free range from -40° to +160°C. withstand long-term (1,000 hours) heat basis of the current portfolio offerings. and can be compounded with large Standard Vamac compounds use car- aging at 150-160°C and short term (168 Besides the monomer ratio, different vis- quantities of halogen-free flame retar- bon black or inorganic fillers for rein- hours) up to ~190°C. Long-term heat cosity grades have been added to improve dant fillers to provide compounds with forcement, which accelerate oxidative aging at 175°C or short term at 200°C, polymer handling and properties, and very low smoke emission and toxicity, degradation. To increase the heat resis- however, exceed the upper temperature also to allow for more flexible compound- which is becoming more and more im- tance, the VMX5000 pre-compounds se- limit, and VMX5000 pre-compounds ing strategies for customers. portant for wire and cable use in the ries utilize a novel filler system that of- present an alternative higher-heat re- The majority of Vamac-brand applica- transportation and/or building sector. fers 10° to 15°C improved heat resistance sistant material before moving to costli- tions are in the automotive sector, where The latest new polymer additions to over conventional carbon black-filled er FKM options. heat and oil resistance are critical. For the Vamac portfolio and compounding AEM or HT-ACM, while maintaining Fig. 2 shows the retained elongation seals and gaskets, fast curing compounds studies related to these three main ap- very good physical properties and fluid at break after different heat aging con- with excellent compression set resistance plication areas are discussed in the fol- resistance. ditions. The VMX5015 compound shows combined with heat and fluid resistance lowing passages. Vamac VMX5000 series pre-compounds improved behavior after long-term aging can be seen as an interesting cost-effec- at 175°C and also short term at 200°C Table 1: DuPont Vamac grades by application areas. tive alternative to FKM materials in the compared to Standard Ultra AEM. A temperature range between -35° and peroxide-cured FKM compound is +175°C, especially when good resistance shown for comparison. to aggressive oil-acid mixtures and good Besides retention of properties after low temperature performance is re- heat or fluid aging, industry standard quired. Fig. 1 shows temperature rating See Polymers, page 20 Fig. 2: Heat aging at different temperatures: Ultra IP vs. VMX5015 and FKM (70ShA). Fig. 1: Temperature rating of VMX5000 pre-compounds vs. Vamac Ultra and HT-ACM. Fig. 3: CSR in air at 165°C: Vamac Ultra IP and VMX5015 vs. HT-ACM. P018_P021_RPN_20201130.indd 18 11/25/20 3:48 PM See Polymers, page 21 www.rubbernews.com www.rubbernews.com Rubber & Plastics News • November 30, 2020 19 Technical nician. In 2003 he joined DuPont at the He also has four patents. DuPont, leading research on Vamac technical center in Geneva as a technical Mark Stewart received his bachelor’s and Hytrel at the Experimental Station New developments in properties representative. He currently works for degree and co-operative education certifi- in Wilmington. He received bachelor’s DuPont in technical service and develop- cate in chemical engineering from Purdue and master’s degrees in chemical engi- ment, and he oversees the testing and University in 1992. He joined DuPont op- neering from Carnegie-Mellon Univer- process laboratory for Vamac. erations at the Sabine River Works eth- sity and the University of Delaware in for ethylene acrylate polymers Ed McBride received a bachelor’s de- ylene unit in Orange, Texas, and in 1995 1980 and 1982, respectively. gree in chemical engineering from the was assigned to ethylene copolymers op- Elias Wang received his bachelor’s in The authors University of Virginia in 1979. He has erations support, including Vamac. chemical engineering and technology worked for DuPont since then in a vari- In 1997, Stewart transferred to the from Shanghai Jiao Tong University in ety of assignments, including manufac- DuPont Experimental Station in Wilm- China in 2003. He joined DuPont China turing, R&D and technical services. He ington to lead the ethylene copolymers R&D Center in 2005 to set up the packag- currently is located in Wilmington and R&D pilot plant operations. After complet- ing and industrial polymer laboratory. He focuses on the Vamac product line. ing certification for Six Sigma Black Belt moved to work on Vamac in a technical McBride has authored or co-authored in 2004, he assumed his R&D role on Va- service and development role from 2008, more than 30 technical papers and has mac elastomers as a principal investigator. and the following year assumed a similar written several chapters in textbooks. Steve Oriani is a technical fellow at role for Viton elastomers. Kammerer Bouvier based on three industry-accepted crite- ria: less than 50 percent loss in tensile strength and elongation at break, and less than 15-point change in Shore A Hardness. McBride Stewart Standard Vamac compounds will withstand long-term (1,000 hours) heat aging at 150-160°C and short term (168 hours) up to ~190°C. Long-term heat aging at 175°C or short term at 200°C, however, exceed the upper temperature Who needs data? Your business! limit, and VMX5000 pre-compounds present an alternative higher-heat re- sistant material before moving to costli- er FKM options. Fig. 2 shows the retained elongation Check out the RUBBER & PLASTICS News’ Data Store for scores of at break after different heat aging con- Oriani Wang ditions. The VMX5015 compound shows improved behavior after long-term aging Patricia Panne rankings AND LISTS THAT CAN HELP YOU RUN YOUR BUSINESS TODAY at 175°C and also short term at 200°C received her doc- compared to Standard Ultra AEM. A torate in chem- peroxide-cured FKM compound is istry from the HERE ARE THE RECENT ADDITIONS TO THE STORE: shown for comparison. University of Co- Besides retention of properties after logne, Germany, heat or fluid aging, industry standard in 2004. After a Global Tire Report: 2020 Top 75 Global Tire See Polymers, page 20 postdoctoral fel- Company rankings. Includes the world’s tire lowship in the Fig. 2: Heat aging at different temperatures: Ultra IP vs. VMX5015 and FKM (70ShA).
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