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2 Table of Contents Page Introduction 1 s in Natural Rubber 2 ZMTI with AGERITE SUPERLITE SOLID in NR 3 ZMTI in Sulfur and Low Sulfur Cures of NR 4 ZMTI as a Copper Inhibitor in Natural Rubber 5 s in EPDM ZMTI in Sulfur-Cured EPDM 6 ZMTI in a Peroxide-cured EPDM Wire & Cable Compound 7 ZMTI in an EPDM Compound 8 s in Neoprene MTI in a Neoprene W Compound 10 MTI in a Neoprene GW Compound 12 s in NBR ZMTI in Peroxide-cured Nitrile 13 ZMTI Synergy in Peroxide-Cured Nitrile 14 ZMTI in Effi cient Vulcanization (EV)-Cured NBR 15 ZMTI in Peroxide-Cured NBR 16 s in HNBR ZMTI in HNBR 17 s in SBR MTI in Mineral-fi lled SBR 18 ZMTI and MTI Specifications 19 Please visit our website for sample requests, sales specifi cations, and Material Safety Data Sheets Winfi eld Street, P.O. Box 5150, Norwalk, CT Telephone: (203) Fax: (203) rubber@vanderbiltchemicals.com TRADEMARKS AGERITE, ALTAX Accelerator, CADMATE Accelerator, CAPTAX Accelerator, DIXIE CLAY Filler, MORFAX Accelerator, NICLATE, TUADS Accelerator, VANAX Accelerator, VANFRE Processing Aid,, VANPLAST Plasticizer and VAROX Peroxide Accelerators are registered trademarks of R.T. Vanderbilt Holding Company, Inc. and/or its respective wholly owned subsidiaries. Chemigum is a registered trademark of Eliochem, Inc. Cure-Rite, Resin D, Stalite, Superfl ex and Superlite are registered trademarks of Emerald Polymers Additives, LLC. Hi-Sil is a registered trademark of PPG Industries. Nipol and Zetpol is a registered trademark of Zeon Corporation. Paraplex is a registered trademark of HallStar Innovations Corp. Responsible Care is a registered trademark of the American Chemistry Council. Songnox is a registered trademark of Songwon Industrial Co., Ltd. Translink is a registered trademark of BASF Catalysts LLC. UL is a registered trademark of Underwriters Laboratories Inc. Vistalon is a trademark of ExxonMobil Corporation. DISCLAIMER Before using, read, understand and comply with the information and precautions in the Safety Data Sheets, label and other product literature. The information presented herein, while not guaranteed, was prepared by technical personnel and, to the best of our knowledge and belief, is true and accurate as of the date hereof. No warranty, representation or guarantee, express or implied, is made regarding accuracy, performance, stability, reliability or use. This information is not intended to be all-inclusive, because the manner and conditions of use, handling, storage and other factors may involve other or additional safety or performance considerations. The user is responsible for determining the suitability of any material for a specifi c purpose and for adopting such safety precautions as may be required. Vanderbilt Chemicals, LLC does not warrant the results to be obtained in using any material, and disclaims all liability with respect to the use, handling or further processing of any such material. No suggestion for use is intended as, and nothing herein shall be construed as, a recommendation to infringe any existing patent, trademark or copyright or to violate any federal, state or local law or regulation. rev09/17/2013
3 ZMTI and MTI Synergistic s maximize a product s resistance to high temperature. Rubber compounds are usually protected by just one antioxidant, but more severe service conditions require combinations of antioxidants. ZMTI is an antioxidant that is manufactured at Vanderbilt Chemicals, LLC plant in Murray, KY. It works particularly well in combination with other antioxidants. Its synergistic effect has been demonstrated with various rubber formulations using polymers such as EPDM, Natural Rubber, Neoprene, NBR and SBR. ZMTI provides excellent protection against heat and oxygen aging, especially when combined with amine or phenolic-type antioxidants, and is also benefi cial where improved fl ex fatigue resistance is required. The synergistic effect of ZMTI with other antioxidants has been demonstrated in both mineral- and carbon black-fi lled compounds, as well as with conventional sulfur, low sulfur, sulfur-donors, or peroxide cure systems. VAROX Peroxide Accelerator cures provide vulcanizates with maximum thermal and oxidative stability, as well as superior resistance to compression set. Most antioxidants reduce peroxide effi ciency, resulting in a loss of physical properties. ZMTI is fully compatible with peroxide cures and gives the best results in combination with amines such as CDPA or AGERITE SUPERFLEX SOLID G. This synergistic combination of antioxidants also offers the best thermal stability and maximum fl ex fatigue resistance in conventional sulfur cure systems. AGERITE STALITE S is the preferred antioxidant for Neoprene. When used with MTI in Neoprene cure systems, the synergistic effect is evident in the improved heat resistance. This combination also improves fl ex fatigue resistance despite providing higher modulus and hardness. In summary, ZMTI and MTI exhibit the following features: Synergy with amines and phenol antioxidants Maximum high temperature resistance Flex fatigue resistance No interference with peroxide cures Nonvolatile Good color 1
4 s in Natural Rubber s are materials that protect rubber against reaction with oxygen. Just a small percentage of oxygen chemically combined with rubber can seriously degrade the physical properties of a rubber part. Heat can signifi cantly increase the rate at which oxygen reacts with rubber; the rate approximately doubles for each 10 degree Centigrade increase in temperature. Compared to room temperature, aging a vulcanizate in a 70ºC oven provides about a 50-fold increase in reaction rate. Work in the Vanderbilt Rubber Laboratory shows that, in general, one day of oven aging at 70ºC corresponds to one year of environmental or shelf aging for natural rubber. The major types of antioxidants are phenols, amines, polymerized quinolines, peroxide decomposers and synergists. Phenols are most effective in non-black compounds and provide minimal discoloration. Amines cause moderate to severe discoloration and are typically used in black-fi lled compounds. Diphenylamine antioxidants are general-purpose antioxidants. Polymerized quinolines are relatively permanent in most polymers and cure systems. Peroxide decomposers are typically used in uncured applications as polymer stabilizers or to protect adhesives. Synergists, such as ZMTI and MTI, increase the performance of other antioxidants. The mechanism by which synergists work is not fully understood, but it may be that they are peroxide decomposers that can survive the vulcanization process. In general, there is a trade-off between the discoloration caused by an antioxidant when exposed to light, and the oxidative protection it provides. While amines are progressively more discoloring than phosphites and phenols, the resistance to oxygen, heat, metal-catalyzed degradation and fl ex fatigue generally improve. For maximum effectiveness, the combination of a radical trap phenol or amine antioxidant with the synergist ZMTI will often be the best means to obtain a high standard of performance. 2
5 ZMTI with AGERITE SUPERLITE SOLID in NR The synergistic effect of ZMTI with a primary antioxidant in Natural Rubber is very evident in the retained elongation property after heat aging. EV Cured Mineral-Filled NR Aged C Tensile Elongation % Retained No AO ZMTI Phenolic AO ZMTI + AO Figure 1: ZMTI Synergy with a Primary in NR Ingredients (phr) Control ZMTI AGERITE SUPERLITE SOLID ZMTI + AO Smoked Sheet NR Stearic Acid Zinc Oxide VANPLAST R Processing Aids DIXIE CLAY Filler Calcium Carbonate Hi-Sil MORFAX Accelerator ETHYL CADMATE Accelerator ZMTI AGERITE SUPERLITE S Totals Press Cured C 300% Modulus, MPa Tensile, MPa Elongation, % Hardness, Shore A TEST TUBE AGED C Tensile Retained, % Elongation Retained, %
6 ZMTI in Sulfur and Low Sulfur Cures of NR In sulfur-cured natural rubber compounds, the addition of 1 phr of ZMTI greatly improves fl ex resistance while also showing an increase in heat stability. A low sulfur-cured natural rubber compound, accelerated by the combination of MORFAX Accelerator and CURE-RITE 18 Accelerator and protected by AGERITE SUPERFLEX SOLID G and 6PPD, develops outstanding fl ex resistance and heat stability. In both conventional and low sulfur-cured compounds, the addition of ZMTI to the antioxidant system greatly improves fl ex resistance while also showing an improvement in heat stability. Compounds (phr) Ingredients: SMR-5 Natural Rubber Stearic Acid Zinc Oxide VANPLAST R Plasticizer N330 Carbon Black Sulfur ALTAX (MBTS) Accelerator METHYL TUADS (TMTD) Accelerator MORFAX Accelerator CURE-RITE 18 Accelerator AGERITE SUPERFLEX SOLID G PPD ZMTI Totals MOONEY 121 C Minimum Viscosity, mu t5, minutes Press Cured C 300% Modulus, MPa Tensile Strength, MPa Elongation at Break, % Tear, Die C, kn/m Hardness, Shore A TEST TUBE AGED C Tensile Retained, % Elongation Retained, % COMPRESSION SET METHOD B C Set, % DEMATTIA FLEX Kilocycles to 1.9 cm <
7 ZMTI as a Copper Inhibitor in Natural Rubber Some antioxidants provide protection to natural rubber when copper contamination is present. The combination of AGERITE STALITE S and ZMTI provides excellent protection against copper deterioration, with minimal discoloration. Ingredients (phr) Control AGERITE STALITE S ZMTI + AGERITE STALITE S SMR Stearic Acid Zinc Oxide DIXIE CLAY Filler Titanium Dioxide Ultramarine Blue ALTAX (MBTS) Accelerator METHYL TUADS (TMTD) Accelerator Sulfur Copper Oleate AGERITE STALITE S ZMTI Totals Press Cured C 500% Modulus, MPa Tensile, MPa Elongation, % Hardness, Shore A TEST TUBE AGED C Tensile Retained, % melted Elongation Retained, % melted Hardness, Pts. Change melted -8-6 OXYGEN BOMB AGED C Tensile Retained, % Elongation Retained, % Hardness, Pts. Change GE BRIGHTNESS Original hrs. exposure to UV light
8 s in EPDM In sulfur-cured EPDM, it is often suffi cient to use only primary antioxidants. However, peroxide curing does require that attention be paid to antioxidant selection because many types of antioxidants can interfere with peroxide crosslinking. Primary antioxidants can donate hydrogen atoms, which compete with the polymer for peroxide radicals and lessen the state of cure. ZMTI is recommended for use in combination with primary antioxidants in peroxide curing because it exhibits minimal interference with the crosslinking mechanism. ZMTI in Sulfur-Cured EPDM Ingredients (phr) No AO AGERITE STALITE S AGERITE RESIN D NDBC ZMTI Vistalon 2504 Ethylene Propylene Diene Stearic Acid Zinc Oxide VANPLAST R Plasticizer N990 Carbon Black N550 Carbon Black Paraffi nic Oil CAPTAX (MBT) Accelerator METHYL TUADS (TMTD) Accelerator Sulfur AGERITE STALITE S AGERITE RESIN D NDBC ZMTI Totals Press Cured C 300% Modulus, MPa Tensile, MPa Elongation, % Hardness, Shore A TEST TUBE AGED C Tensile Retained, % Elongation Retained, % Hardness, Pts. Change TEST TUBE AGED C Tensile Retained, % Elongation Retained, % Hardness, Pts. Change TEST TUBE AGED C Tensile Retained, % Elongation Retained, % Hardness, Pts. Change
9 ZMTI in a Peroxide-Cured EPDM Wire & Cable Compound When half of AGERITE RESIN D is replaced with ZMTI in a peroxidecured EPDM compound, the combination develops outstanding heat resistance at 150ºC. EPDM Wire and Cable Compound Aged C Tensile Elongation % Retained No AO AGERITE RESIN D ZMTI ZMTI + AGERITE RESIN D Figure 2: s in Peroxide-Cured EPDM ZMTI ZMTI + Ingredients (phr) No AO AGERITE RESIN D AGERITE RESIN D Vistalon 2504 Ethylene Propylene Diene VANFRE AP-2 Processing Aid Zinc Oxide N990 Carbon Black Translink Paraffi nic Oil Silane A Red Lead VAROX DCP-40KE Peroxide Accelerator AGERITE RESIN D ZMTI Totals MOONEY 132 C Minimum Viscosity, mu t5, minutes Press Cured C 300% Modulus, MPa Tensile, MPa Elongation, % Hardness, Shore A TEST TUBE AGED C Tensile Retained, % Brittle Elongation Retained, % Brittle Hardness, Pts. Change Brittle
10 ZMTI in an EPDM Compound The selection of an antioxidant system that optimizes the physical properties of the fi nished product is extremely important in rubber compounding. The effectiveness of several antioxidants was compared in peroxide-cured EPDM. ZMTI works syner-gistically with other antioxidants to greatly improve the retention of physical properties. ZMTI by itself was found to be the best performing antioxidant, having the highest heat aged retention and lowest compression set. The addition of AGERITE RESIN D or CDPA Solid to ZMTI provides the compounder with further high performance options. Peroxide-Cured EPM/EPDM General-Purpose Compound Aged C 110 Tensile Elongation % Retained No AO AGERITE CDPASolid RESIN D ZMTI ZMTI + AGERITE RESIN D ZMTI + CDPASolid Figure 3: Performance of an EPDM Compound Vanderbilt Chemicals, LLC offers the following product options with regard to compounding requirements: ZMTI alone has the best elongation retention and compression set resistance. AGERITE RESIN D alone is a good cost-effective option. CDPA Solid alone has good overall results. ZMTI and AGERITE RESIN D together provide the best tensile retention. ZMTI and CDPA Solid together provide the best overall results. 8
11 ZMTI in an EPDM Compound Ingredients (phr) No AO AGERITE RESIN D CDPA Solid ZMTI ZMTI + AGERITE RESIN D ZMTI + CDPA Solid Vistalon 706 Ethylene Propylene Diene Vistalon 7500 Ethylene Propylene Diene N550 Carbon Black Paraffi nic Oil VAROX KE Peroxide Accelerator VANAX MBM PWDR Accelerator ZMTI CDPA Solid AGERITE RESIN D Totals Press Cured t C 100% Modulus, MPa Tensile Strength, MPa Elongation, % Hardness, Shore A OVEN AGED C Tensile Retained, % Elongation Retained, % OVEN AGED C Tensile Retained, % Elongation Retained, % COMPRESSION SET METHOD B C Set, %
12 s in Neoprene Polychloroprene An amine antioxidant is standard in most formulations of both G and W types of Neoprene. The Neoprene G types have inherently good strength and fl ex fatigue resistance, while the Neoprene W types offer improved heat and compression set resistance. MTI, when used in addition to the amine AGERITE STALITE S, will improve the heat and fl ex resistance of both G and W types of Neoprene. 100 MTI in a Neoprene W Compound 200 % Retained Kilocycles 0 No AO 2 AGERITE STALITE S 2 AGERITE STALITE S + MTI 1 AGERITE STALITE S + 1 MTI 0 Figure 4: MTI in Neoprene W Ingredients (phr) No AO AGERITE STALITE S 1 AGERITE STALITE S + 1 MTI 2 AGERITE STALITE S + 1 MTI Neoprene W Polychloroprene Stearic Acid Magnesium Oxide N774 Carbon Black Naphthenic Oil VANPLAST PL Plasticizer Zinc Oxide VANAX CPA Accelerator AGERITE STALITE S MTI Totals
13 MTI in a Neoprene W Compound Compounds No AO AGERITE STALITE S 1 AGERITE STALITE S + 1 MTI 2 AGERITE STALITE S + 1 MTI MOONEY C Minimum Viscosity, mu t5, minutes ºC, 0.5 Arc Min. Torque, M L, dn m Max. Torque, M H, dn m t s 1, minutes t 90, minutes Press Cured t C 200% Modulus, MPa Tensile Strength, MPa Elongation, % Hardness, Shore A OVEN AGED C Tensile Retained, % Elongation Retained, % Hardness, Pts. Change COMPRESSION SET METHOD B C Set, % DEMATTIA FLEX Kilocycles to 1.9 cm
14 MTI in a Neoprene GW Compound Ingredients (phr) No AO AGERITE STALITE S AGERITE STALITE S + MTI Neoprene GW Polychloroprene Stearic Acid Magnesium Oxide N774 Carbon Black Naphthenic Oil VANPLAST PL Plasticizer Zinc Oxide AGERITE STALITE S MTI Totals MOONEY C Minimum Viscosity, mu t5, minutes ºC, 0.5 Arc Min Torque, M L, dn m Max Torque, M H, dn m t s 1, minutes t 90, minutes Press Cured t C 300% Modulus, MPa Tensile Strength, MPa Elongation, % Hardness, Shore A OVEN AGED C Tensile Retained, % Elongation Retained, % Hardness, Pts. Change COMPRESSION SET METHOD B C Set, % DEMATTIA FLEX Kilocycles to 1.9 cm
15 s in NBR Due to the unsaturation in their polymer backbone, nitrile compounds require antioxidants to combat the degradation caused by high temperatures. These antioxidants may also need extraction resistance since NBR compounds are often used in oils and solvents. ZMTI is the recommended antioxidant for heat stability in nitrile rubber. It can be used with good results alone or in combination with AGERITE RESIN D, AGERITE STALITE S or CDPA Solid. ZMTI in Peroxide-Cured Nitrile Ingredients (phr) AGERITE RESIN D AGERITE STALITE S METHYL NICLATE Dustless Special ZMTI Chemigum N Paraplex G N990 Carbon Black N550 Carbon Black VAROX DCP-40KE Peroxide Accelerator AGERITE RESIN D AGERITE STALITE S METHYL NICLATE Dustless Special ZMTI Totals MOONEY 121 C Minimum Viscosity, mu t5, minutes Press Cured C 100% Modulus, MPa Tensile, MPa Elongation, % Hardness, Shore A TEST TUBE AGED C Tensile Retained, % Elongation Retained, % Hardness, Pts. Change COMPRESSION SET METHOD B C Set, %
16 ZMTI Synergy in Peroxide-Cured Nitrile Ingredients (phr) AGERITE RESIN D + ZMTI AGERITE STALITE S + ZMTI METHYL NICLATE Dustless Special + ZMTI Chemigum N Paraplex G N990 Carbon Black N550 Carbon Black VAROX DCP-40KE Peroxide Accelerator AGERITE RESIN D AGERITE STALITE S METHYL NICLATE Dustless Special ZMTI Totals MOONEY 121 C Minimum Viscosity, mu t5, minutes Press Cured 20 C 100% Modulus, MPa Tensile, MPa Elongation, % Hardness, Shore A TEST TUBE AGED 72 C Tensile Retained, % Elongation Retained, % Hardness, Pts. Change COMPRESSION SET METHOD B C Set, %
17 ZMTI in Efficient Vulcanization (EV)-Cured NBR 65 Heat Resistance in EV Cured NBR 20 % Set MPa 40 No AO 3 3 CDPA CPDA Solid 22 CDPA CDPA Solid 1 CDPA CDPA Solid 1 ZMTI 2 ZMTI 3 ZMTI 0 Compression Set Aged Tensile Strength Figure 5: ZMTI in EV-Cured NBR Ingredients (phr) No AO CDPA Solid CDPA Solid + ZMTI (2:1) ZMTI + CDPA Solid (2:1) ZMTI Nipol DN Nipol DN Zinc Oxide Stearic Acid N774 Carbon Black DOP METHYL TUADS (TMTD) Accelerator CDPA Solid ZMTI Totals Press Cured t C 200% Modulus, MPa Tensile Strength, MPa Elongation, % Hardness, Shore A OVEN AGED C Aged Tensile Strength, MPa Aged Elongation, % Brittle Brittle Hardness, Pts. Change COMPRESSION SET METHOD B ºC Set, %
18 ZMTI in Peroxide-Cured NBR 50 Compression Set and Flex Resistance in Peroxide-Cured NBR 800 % Set Kilocycles 25 No AO 3 3 CDPA CDPA Solid 2 CDPA Solid 1 CDPA Solid 1 ZMTI 2 ZMTI 3 ZMTI 0 Compression Set DeMattia Flex Fatigue Ingredients (phr) Figure 6: ZMTI in a Peroxide-Cured NBR No AO CDPA Solid CDPA Solid+ ZMTI (2:1) ZMTI + CDPA Solid (2:1) ZMTI Nipol DN Zinc Oxide Stearic Acid N774 Carbon Black DOP VAROX DCP-40KE CDPA Solid ZMTI Totals Press Cured t C 200% Modulus, MPa Tensile Strength, MPa Elongation, % Hardness, Shore A COMPRESSION SET METHOD B C Set, % DEMATTIA FLEX Kilocycles to 1.9 cm
19 s in HNBR HNBR rubber is nitrile rubber which has been hydrogenated to reduce the number of carbon-carbon double bonds. The saturation improves the heat and ozone resistance of nitrile in HNBR. All HNBR rubber can be peroxide-cured to provide the most heat resistant cure system. ZMTI in HNBR CDPA Solid Ingredients (phr) No AO CDPA Solid + ZMTI Zetpol Zinc Oxide Stearic Acid N330 Carbon Black N990 Carbon Black CDPA Solid ZMTI VAROX DCP-40KE Total MOONEY 121 C Minimum Viscosity, mu t5, minutes Press Cured t C 200% Modulus, MPa Tensile, MPa Elongation, % Hardness, Shore A OVEN AGED C Tensile Retained, % Elongation Retained, % Hardness, Pts. Change OVEN AGED C Tensile Retained, % Elongation Retained, % Hardness, Pts. Change COMPRESSION SET METHOD B C Set, %
20 s in SBR While all SBR polymers contain some antioxidant, it is considered good compounding practice to include an antioxidant in each formula, particularly when compounding for heat resistance and heavy duty service. Certain amines, like AGERITE SUPERFLEX SOLID G, are known to inhibit gel formation in hot mixing, and are used in black compounds to assure uniform extrusion and calendering. MTI or phenols like SONGNOX 3114 are often used in non-black compounds. MTI in Mineral-Filled SBR Ingredients (phr) No AO MTI SONGNOX 3114 SBR VANFRE AP-2 Processing Aid Stearic Acid Zinc Oxide VANPLAST R Plasticizer DIXIE CLAY Filler Sulfur ALTAX (MBTS) Accelerator METHYL TUADS (TMTD) Accelerator MTI SONGNOX Totals Press Cured ºC Tensile Strength, MPa Elongation at Break, % Hardness, Shore A OVEN AGED ºC Tensile Retained, % Elongation Retained, % Hardness, Pts. Change GE BRIGHTNESS Original hrs. exposure to UV light
21 ZMTI Specifications RTV Product Code: Composition: Zinc 2-mercaptotolumidazole Physical State: White to light tan powder Specifi cation Test Method *Fineness, through 200 mesh 99.9% minimum T-14D *Heat Loss C 2.0% maximum T-1A *Zinc Content % T-365, AA-103 GENERAL INFORMATION Typical values not routinely measured or reported on the Certifi cate of Analysis. Anti-Dusting Agent Content 3-5% Density at 25 C 1.54 Mg/m 3 Melting Point, Initial 300 C minimum Solubility - Soluble in ethanol and methanol. Practically insoluble in other organic solvents and water. *Certifi ed Property Uses - A nondiscoloring, nonstaining antioxidant for NR and SR. Particularly effective in EPDM and Nitrile stock. Suggested as a synergist with AGERITE STALITE S, AGERITE RESIN D, and AGERITE SUPERFLEX SOLID G for aging at normal or elevated temperatures. Offers excellent fl ex resistance in NR. RTV Product Code: Composition: 2-mercaptotoluimidazole Physical State: White to off-white powder MTI Specifications Specifi cation Test Method *Ash Content 0.5% maximum T-4 *Assay 97% minimum T-719 *Fineness, through 100 mesh 99.9% minimum T-14 *Heat Loss, 2 hrs at C 1.0% maximum T-1A *Melting Point, Initial 250 C minimum T-3B GENERAL INFORMATION Typical values not routinely measured or reported on the Certifi cate of Analysis. Density at 25 C 1.33 Mg/m 3 Solubility - Moderately soluble in acetone and alcohol. Insoluble in water. *Certifi ed Property Uses - A non-discoloring, non-staining antioxidant for natural and synthetic rubbers. Suggested as a synergist with AGERITE STALITE S, AGERITE SUPERFLEX SOLID G and AGERITE RESIN D. 19
22 Vanderbilt Chemicals, LLC 30 Winfield Street, P.O. Box 5150 Norwalk, CT (203) Fax: (203) vanderbiltchemicals.com Vanderbilt Chemicals, LLC 6281 Beach Boulevard, Suite 204 Buena Park, California (714) Fax: (714) vanderbiltchemicals.com U L Vanderbilt Chemicals, LLC ISO 9001: rev09/17/2013
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