Improved heat and ozone resistant NBR/epichlorohydrin blends

Abstract: Cured blends of acrylonitrile/butadiene (NBR)/epichlorohydrin rubbers are provided that are free of poisonous lead compounds with ozone resistance of 10 hours or more and good heat resistance and fuel and oil resistance. These acrylonitrile/butadiene rubbers contain 28 to 33% by weight of acrylonitrile. The epichlorohydrin rubbers are useful in this invention which contains at least 4 to 12% of allyl glycidyl ether and may contain 0 to 35% of ethylene oxide, preferably 2 to 6% and up to 15%. The acrylonitrile/butadiene rubber is preferably of so-called bound antioxidant type which contains about 1 to about 10% by weight of polymerized attached antioxidant containing monomer.

Description: Technical Fields This invention relates to a method of producing a more economical homogenous vulcanized blend of acrylonitrile butadiene rubber and epichlorohydrin rubber that exhibits physicals equal to those of the individual rubbers or superior thereto. More specifically, this invention provides a homogenous blend of modified epichlorohydrin rubber and acrylonitrile-butadiene bound antioxidant terpolymer and rubber that is cheaper than 100% epichlorohydrin rubber but with physicals equivalent or better than epichlorohydrin rubber and free of harmful lead compounds. Background Art Although epichlorohydrin rubbers and acrylonitrile-butadiene rubbers are polar, their polarity and compatibility are different. Consequently, their blends are generally considered incompatible and their blends exhibit low ozone resistance unless cured with a lead curative but lead cured rubbers are objectionable for harm to the environment. Further, these rubbers need different cure systems and degrade by different mechanism. For example, epichlorohydrin rubbers degrade with oxidation through a reversion mechanism while acrylonitrile-butadiene rubber undergoes resinification as it oxidizes. Further, the resinification degradation is harmful to use in fuel and oil application. Therefore, it has been desirable to produce blends of these rubbers that have good to superior ozone resistance, better heat aging and resistance to fuel and oil, and freedom from lead curatives. GB-B-1 246 039 teaches how to obtain good ozone resistance of vulcanized blends of acrylonitrile butadiene rubber and epichlorohydrin rubber cured with lead compounds; however, these vulcanizates contain undesirable lead compounds that present problems. Chemical Abstracts, vol. 81, no. 10, 9 Sept. 1974, Columbus, Ohio, USA, abstract no. 50821 discloses epihalohydrin elastomer vulcanizates with good compression and oil resistance prepared by vulcanizing 100 parts of an elastomer composition comprising epihalohydrin elastomer, natural rubber and(or) synthetic rubber in the presence of 0.1-5.0 parts of S or a mixtures of S and a S-containing compound and 0.1-7.0 parts of a sulfenamide or a mixture of a sulfenamide and thiocarbamate. Disclosure of Invention The invention solves the above mentioned problems with the blend as described in the appended claims. The modified acrylonitrile-butadiene rubber and the modified epichlorohydrin rubbers can be blended in the usual and conventional Banbury or mill equipment to give a homogenous blend which has cured physical equivalent or better than the physicals of the individual components of the blend and at a lower cost than 100% epichlorohydrin rubber and without use of harmful lead curatives. Also, these modified blends can be cured to yield a compatible blend with enhanced tensile, compression set, ozone resistance, heat ageing and resistance to fuel and oil. The modified epichlorohydrin rubbers may be copolymers but preferably are ter- polymers of the epichlorohydrin monomer with allyl glycidal ether (AGE) and ethylene oxide. AGE is used to yield the copolymer or preferably with ethylene oxide to yield the terpolymer of epichlorohydrin. Preferably these modified epichlorohydrin rubbers contain from about 4% to about 12% AGE by weight and may contain from o to 35 but preferably 15 or more percent ethylene oxide. The modified acrylonitrile-butadiene rubbers useful in this invention contain a Mooney plasticity ML-100°C/4' of 20 to 65, and preferably of 25 to 50 and an acrylonitrile content of 28 to 33% by weight. The acrylonitrile-butadiene polymers available under the trade name CHEMIGUM® N765 which contains 28% acrylonitrile and CHEMIGUM® HR665 and CHEMIGUM® HR662 which have 33% acrylonitrile are useful in this invention. The necessary cure system will also cure both the modified acrylonitrile-butadiene rubber and the modified epichlorohydrin rubbers simultaneously. The resulting cured blends have superior ozone resistance when the epichlorohydrin, is Hydrin TX-1 that is a terpolymer containing 12% AGE, relative to epichlorohydrin, Hydrin T with 4% AGE. These modified epichlorohydrin rubbers have Mooney plasticity ML-100°C/4' of about 60 to 110 and preferably 60-90. Use of modified acrylonitrile-butadiene rubber of 28 to 33% acrylonitrile content with 4 to 12% AGE modified polymer of epichlorohydrin rubbers preferably the ter- polymer in my blends allows the blends to be cured with sulfur cures and peroxide cure system, although the peroxide cure system gives far superior ozone resistance. It should be explained that the use of a modified soap/calcium oxide and peroxide/co-agent cure systems, as shown in Table III , gives better ozone resistance relative to a low sulfur EV type cure. Not only are superior ozone resistance properties enhanced, other physicals such as tensile strength, scorch resistance, tear strength, compression set resistance, and abrasion resistance are enhanced. Also, oil and fuel resistance of my blends are essentially equivalent to the 100% epichlorohydrin and allowance of the blends to be used for products that come in contact with fuel oil and related chemicals. The well-known bound antioxidant acrylonitrile butadiene rubbers are especially preferred in this invention as they offer greatly improved resistance to degrading by resinification which has been a problem with exposure to hot fuels and oils. These bound antioxidant acrylonitrile/butadiene rubbers are usually made by dissolving the bound antioxidant monomer such N(4-anilinophenyl) methacrylamide in small amount of the acrylonitrile and the solution is pumped into the usual polymerization mixture of acrylonitrile and butadiene as explained in Table II of James W. Horvath' s article " Bound Antioxidants Stabilized NBR in Automobile Applications ", Elastomerics, August 1979, pp 19-62. The nature of these monomers useful for preparing bound antioxidant acrylonitrile/butadiene polymers are further described in the article by R.H. Kline , presented at the meeting of the Rubber Division, American Chemistry Society, Toronto, Canada, May 7-10, 1974. Specifically these monomers belong to the two classes of phenolic and amine types polymerizable unsaturated monomer. The above two references are incorporated herein to supply the disclosure of these monomers and their bound antioxidant acrylonitrile/butadiene rubbers produced therefrom. The nature of this invention and its advantages are further disclosed and illustrated by the following illustrative and exemplar examples where all parts are by weight unless otherwise indicated. Standard ASTM test procedures were used throughout the testing, except where indicated. ASTM D 3182 was used for sample preparation, ASTM D 2084 for vulcanization characteristics, ASTM D 412 for physical properties, ASTM D 295 for Compression Set, and ASTM D 471 for fluid aging. Ozone testing was done in an Orec Ozone Chamber at 50 pphm ozone concentration at 38°C. Bent Loop and 20% Stretched Samples were studied. Polymer blends were prepared without high temperature mixing. The polymers were first blended for 1 minute in the Banbury before other ingredients were added. Curatives were again added in a second Banbury pass. No special mix precautions or procedures were attempted in mixing the blends to either prevent or encourage filler or curative migration from one polymer phase to another. The initial screening of epichlorohydrin and acrylonitrile-butadiene bound antioxidant terpolymer blends was done in black loaded compounds using peroxide cure systems which were modified somewhat to attempt to cure both polymer phases uniformly. These formulations and associated data are listed in the following Tables. Epichlorohydrin homopolymers and copolymers are not recommended for blend work as they are not as satisfactory as the terpolymer. The terpolymer Hydrin T containing 24% chlorine and 5% allylglycidyl ether, AGE with ethylene oxide which are capable of sulfur or peroxide curing is especially preferred. A newer terpolymer Hydrin TX-1 containing 29.5% chlorine and 11% AGE was found to be more suitable for blends. Ozone resistance of ten (10) days was not achieved in any of the sulfur cured compounds. The peroxide cured formulations containing CHEMIGUM HR 765A and CHEMIGUM HR 665 and Hydrin T and TX-1 epichlorohydrin terpolymers produced ozone resistant compounds passing ten (10) days aging whereas other samples containing less AGE failed within three (3) days. The CHEMIGUM HR 765A and CHEMIGUM HR 665 blends exhibited no ozone cracking through 10 days of aging in Bent Loop testing with Hydrin TX-1 indicating a greater degree of blend compatibility. The epichlorohydrin terpolymers retained 30 to 38% of their properties after 168 hours at 150°C with silica loading but the blends retained only 5 to 8% in the wholly black loaded compounds. This situation is improved by switching to mineral filled compounds rather than all black; See Table V. The retention in physical properties of the mineral filled compound is 30% after aging 168 hours at 150°C. Further improvement would be expected with improved stabilization additives. The silica or siliceous containing fillers are most desired for good heat aging. As previously indicated, many of the physical properties of the blends were either improved or remained close to those of the epichlorohydrin terpolymers. Tensile strength was improved by blending with acrylonitrile butadiene bound antioxidant terpolymer. Compression Set resistance was better with the 11% AGE epichlorohydrin polymer than the 5% AGE elastomer. Abrasion resistance was significantly improved in both the DIN and Taber Abrasion tests. Fuel resistance was not adversely affected, although nitrile rubbers are not as fuel resistant as epichlorohydrin terpolymers. Oil resistance was only moderately changed, and the blends performed well in ATF Fluid aging and were satisfactory for use in air intake duct hose and selected hose under the hood of a car. Processability of the blends was also greatly improved over that of the pure epichlorohydrin polymers which have a poor reputation for processing in factory environments. They tend to be soft and sticky due to their thermoplastic nature. Blending with bound antioxidant terpolymers allowed them to process without any difficulty in handling and curing. The following tabulation data is presented to further exemplify the nature of this invention. CURED PHYSICAL PROPERTIES I II Specific Gravity 1.285 1.291 Cured Physical Properties Tensile, MPa 13.9 15.2 % Elongation 263 305 300% Modulus 14.9 Shore A Hardness 66 67 Tear Strength, Die C, kg/cm 21.1 26.4 Ozone Aging, 50 pphm, 38°C Bent Loop, days passed without cracking 3 3 20% Stretched Samples, days passed without cracking 10 10 It should be noted that higher percent acrylonitrile rubber gave the better tear resistance and tensile. CURED PHYSICAL III IV V Specific Gravity 1.285 1.294 1.297 Cured Physical Properties Tensile, MPa 13 16 16.3 % Elongation 214 223 274 Shore A Hardness 68 67 68 Tear Strength, Die C, kg/cm 20 19.3 24.3 Ozone Aging, 50 pphm, 38°C Bent Loop, days passed without cracking 3 10 10 20% Stretched Samples, days passed without cracking 10 10 10 The use of relatively high black loading adversely effected the heat aged properties relative to oil, and fuel but replacement of all or part of black with mineral fillers gave better heat ageing properties. Replacing part of the black with 35 parts per hundred of silica in the table caused the cured samples to pass the standard for properties when the cured rubber was tested in hot ageing in fuel and oil. In Table VI blend Nos. A5 and B5 are compared with 100% CHEMIGUM HR662 viz. No. C5 to show the superior ozone resistance of the blends relative to 100% CHEMIGUM 662 . Thus, the blends of the CHEMIGUM 662 , acrylonitrile/butadiene rubbers, and epichlorohydrin passed the ozone resistance test and was able to be used where ozone resistance is needed. 347003 Original Properties Tensile, PSI 1164 Elongation, % 477 100% Modulus 509 200% Modulus 651 300% Modulus 795 Hardness, Shore A 78 Tear, Die(C) PPI 182 Compression Set 70 Hrs @ 212°F Average 37.40 Circ. Air Oven Aging - 70 Hrs @ 257°F Tensile, PSI 1075 % Change -8 Elongation, % 313 % Change -34 100% Modulus 729 Hardness, Shore A 80 Point Change 2 Static Ozone Box 50 pphm 104°F D-1171 Rating @ 3 Days Pass Fluid Aging 70 Hrs at 300°F, ASTM No 3 Oil Tensile, PSI 1023 % Change -12 Elongation, % 255 % Change -47 Hardness, Shore A 78 Point Change 0 Vol. Swell, % 1.9 Fluid Aging 48 Hrs at RT F, ASTM Ref Fuel C Tensile, PSI 720 % Change -38 Elongation, % 385 % Change -19 Hardness, Shore A 57 Point Change -21 Vol. Swell, % 27.8 Table VIII shows properties of a 60% epichlorohydrin blend with 40% acrylonitrile/butadiene with bound antioxidant cured with high silica loading viz mistron vapor, Hi-Sil 532EP and Hi-Sil 243LD with 10 part carbon black at various cure conditions. This table also shows hot fluid aging results needed for hose or belt use under the hood of a vehicle. While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the scope of the claims.

Claims: A blend characterized of modified acrylonitrile-butadiene rubber and a modified epichlorohydrin rubber, said acrylonitrile-butadiene containing from 28% to 33% by weight of acrylonitrile and is present in blend in 90% to 10% by weight and said modified epichlorohydrin being selected from the class consisting of a copolymer of epichlorohydrin and allyl glycidal ether (AGE) and a terpolymer of epichlorohydrin, allyl glycidal ether and ethylene oxide, said allyl glycidal ether being present in the modified epichlorohydrin in an amount of 4 to 12% by weight and is present in blend in 10 to 90% by weight and the ethylene oxide being present in terpolymer in 15 to 35% by weight. The blend of claim 1 characterized in that said acrylonitrile-butadiene is present in blend from 75% to 25% by weight and said modified epichlorohydrin is present in blend from 25 to 75% by weight. The blend of claim 1 or 2 characterized by being cured with a peroxide curative. The blend of claim 1 or 2 characterized by the blend containing 50 to 10% by weight of modified epichlorohydrin polymer and 50 to 10% by weight modified acrylonitrile/butadiene polymer. The blend of claim 4 characterized by the blend being loaded with silica. The blend of claim 2 and 3 characterized by a loading of at least 50% by weight of a mineral filler. The blend of claim 2 characterized by the epichlorohydrin rubber containing 29% or more by weight chlorine and at least 11% by weight of AGE.

Inventors: HORVATH JAMES WALTER, HORVATH, JAMES WALTER
Applicants: GOODYEAR TIRE & RUBBER, THE GOODYEAR TIRE & RUBBER COMPANY
Application year: 1995
Main classification: C08L9
IPC codes: C08L9, C08L71, C08K3, C08L21