GB2028837A - Curable blends of butadiene/acrylonitrile polymer and ethylene copolymer - Google Patents

Curable blends of butadiene/acrylonitrile polymer and ethylene copolymer Download PDF

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GB2028837A
GB2028837A GB7929733A GB7929733A GB2028837A GB 2028837 A GB2028837 A GB 2028837A GB 7929733 A GB7929733 A GB 7929733A GB 7929733 A GB7929733 A GB 7929733A GB 2028837 A GB2028837 A GB 2028837A
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

Curable blends of 100 parts of a butadiene/acrylonitrile polymers with 3-100 parts of ethylene/carbon monoxide or sulfur dioxide copolymers containing 3-25% of CO or SO2 and 10-65% of an additional softening copolymerizable comonomer selected from vinyl esters, alkyl acrylates and methacrylates, alkyl vinyl ethers, acrylonitrile and methacrylonitrile, have improved processing properties, reduced cost, and superior permanence, oil resistance and aging resistance.

Description

SPECIFICATION Curable blends of butadiene/acrylonitrile polymer and ethylene copolymer BACKGROUND OF THE INVENTION Field of the invention This invention reiates to curable blends and more specifically it relates to improved curable blends of acrylonitrile polymer and ethylene copolymer.
Description of the Prior Art Elastomers are frequently compounded with softeners and plasticizers to extend their applicability to different end uses. Many of these softeners are liquids which can volatilize on exposure of the compound to elevated temperatures or can be extracted when the compound is exposed to solvents or oils. More permanent polymeric liquid plasticizers are relatively expensive.
Research Disclosure No. 1381 6, dated October 1975, discloses that the oil resistance of chlorosulfonated polyethylene was, found to be significantly improved for blends in which a terpolymer (30-45 wt. % terpolymer based on the elastomer) of ethylene/carbon monoxide/vinyl acetate was used in place of ethylene/vinyl acetate copolymer. It is also stated therein that sealants with excellent tack and rubberiness were obtained with blends of an ethylene/carbon monoxide/vinyl acetate terpolymer with butyl rubber.
U.S. 3,780,140 discloses terpolymers of ethylene/carbon monoxide/termonomer and blends of same with a compatible amount of at least one solid organic polymer. Various termonomers are disclosed, such as unsaturated mono- and dicarboxylic acids, esters of such acids, vinyl esters of saturated carboxylic acids, vinyl alkyl ethers, acrylonitrile, etc. Solid organic polymers are disclosed to have preferably polar characteristics in order to obtain compatibility on a molecular scale.Such polymers can be polyamides: cellulose derived polymers; vinyl halide polymers; alpha-olefin based polymers such as polyethylene, polypropylene, chlorosulfonated polyethylene; ethylene-vinyl ester copolymers; polymers of styrene; polymers of acrylonitrile and copolymers of at least 40% acrylonitrile and other ethylenically unsaturated comonomers such as vinyl acetate, vinyl chloride and isobutylene; acrylics, polyesters; polyurethanes; polycarbonates; phenolics; polysulfones; epoxy resin; chlorinated polyethers; alkyd resins; acetal resins; ABS resins; silicone resins; tars; waxes; etc.
U.S. 2,495,286 discloses copolymers of ethylene and carbon monoxide with one or more additional polymerizable organic compound such as other olefins, butadienes, vinyl and vinylidene compounds, vinyl esters, styrene, acrylic and methacrylic acids and their esters, etc.
U.S. 3,873,494 discloses curable blends and vulcanizates of 100 parts of an ethylene/alkyl acrylate or alkyl methacrylate copolymer or an ethylene/alkyl acrylate or methacrylate terpolymer wherein the termonomer among others can be carbon monoxide, with 1-30 parts of a butadiene/acrylonitrile polymer. The termonomer is present in an amount not higher than about 10 wt.
% of the terpolymer.
SUMMARY OF THE INVENTION According to the present invention there is provided a curable blend of (a) 100 parts of a butadiene/acrylonitrile polymer containing about 20-50 weight % of acrylonitrile and (b) about 3-1 O0 parts of an ethylene copolymer selected from the group consisting of ethylene/carbon monoxide/X and ethylene/sulfur dioxide/X copolymers, wherein comonomer X is (i) a vinyl ester of an alkanoic acid, the acid having 1 to 18 C atoms, (II) an alkyl acrylate or methacrylate, the alkyl group having 1 to 18 C atoms, (III) alkyl vinyl ether, the alkyl group having 1 to 4 C atoms, (IV) acrylonitrile or methacrylonitrile, or combinations of the above comonomers, the ethylene copolymer containing about 3-25 weight % of carbon monoxide or sulfur dioxide, about 10-65 weight % of comonomer X, and about 3075 weight % of ethylene.
Further provided according to the present invention are compositions comprising the above curable blends combined with peroxide or sulfur curing system.
Still further provided according to the present invention are vulcanized products obtained by heating the combination of the above indicated curable blends and peroxide or sulfur curing systems.
Detailed Description of the Invention It has been found that the modification of curable blends of butadiene/acrylonitrile polymers with an ethylene/carbon monoxide or sulfur dioxide copolymer containing at least one additional softening copolvmerizable comonomer such as a vinyl ester, alkyl acrylate or methacrylate, acrylonitrile, etc., resulrs in vulcanizates with improved processing, reduced cost and compared to modification with low molecular weight modifiers, superior permanence in softened compounds, oil resistance, aging resistance.
As a result of the above indicated improved characteristics these modified vulcanizates can be employed in extruded shapes, such as tubing, gasketing, and electrical cable coverings; in composite structures such as fabric-reinforced hose, belting, and coated sheet; in shoe soling compounds, including cellular materials; and miscellaneous molded goods such as seals and O-rings.
The solid butadiene/acrylonitrile polymer (nitrile rubber) which is the main component of the blends of the present invention is a well-known material. It can be made, for example, by free radical initiated copolymerization of butadiene and acrylonitrile either in solution or in emulsion, by methods known in the art. The molecular weight of the material should be such that they exhibit Mooney Viscosities (ML-4, 1000C) of about 2 > 120. It is not intended to limit suitable butadiene/acrylonitrile polymers to bipolymers; terpolymers such as, for example, carboxylated butadiene/acrylonitrile polymers can also be used. These are made by copolymerization of butadiene, acrylonitrile and a polymerizable carboxylic acid, for instance acrylic acid or methacrylic acid.For practical purposes, suitable butadiene/acrylonitrile polyners are available commercially, including grades which have been preblended with polyvinyl chloride resin.
The proportion of acrylonitrile in the polymer is generally about 20-50 weight %, the preferred proportion being about 25-41 weight %, such polymers giving optimum balance of elastomeric properties and resistance to fluids.
The ethylene copolymer modifier of the present invention is an ethylene carbon monoxide or sulfur dioxide copolymer containing at least one additional softening copolymerizable comonomer such as (a) vinyl esters of an alkanoic acid, the acid having 1 to 1 8 carbon atoms, e.g., viny formate, vinyl acetate, and vinyl stearate (b) alkyl acrylates or methacrylates, the alkyl group having 1 to 1 8 carbon atoms, e.g., methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethylhexyl acrylate, and stearyl acrylate (c) alkyl vinyl ether, the alkyl group having 1 to 4 carbon atoms, e.g., methyl vinyl ether (d) acrylonitrile or methacrylonitrile, or combinations of the above comonomers.
The carbon monoxide or sulfur dioxide component of the ethylene copolymer of the present invention should be present n the amount of about 3-25 weight %, preferably about 6-1 5 weight %.
The additional softening copolymerizable comonomer component of the ethylene copolymer of the present invention can be present in about 1 W65 weight %, preferably about 2S35 weight %.
The amount of ethylene in the copolymer should be about 30-75 weight %, preferably about 50 to 70 weight %.
In these copolymers, copolymerized carbon monoxide or sulfur dioxide confers a high degree of polarity to the polymer without unduly reducing the ethylene content of the polymer. For instance, 1 weight % of copolymerized carbon monoxide confers polarity to the polymer equivalent to 3 to 5 weight % of a representative comonomer X, e.g., vinyl acetate, methyl acrylate, or 2-ethylhexyl acrylate.This property is important for several reasons: (a) at relatively high ethylene content, such polymers have sufficient polarity to be compatible with the nitrile rubber, (b) at a given level of polarity, copolymers containing copolymerized CO or SO are less sticky than those which contain only ethylene and comonomer X and are thus more easily processed because of reduced sticking to the surfaces of processing equipment, (c) in addition to compatibility considerations, polarity is necessary to maintain resistance of the nitrile rubber blends and vulcanizates to fluids such as fuels and oils.
The amount of ethylene copolymer in the blends of the present invention is about 3-1 00 parts, preferably about 5-50 parts, per 100 parts of butadiene/acrylonitrile polymer.
The butadiene/acrylonitrile polymer including grades modified with polyvinyl chloride resin, and the ethylene copolymer can be mixed uniformly with any of the usual mixing devices such as a roll mill, extruder, Banbury mixer, or other internal mixing device which is capable of mixing the materials without undue heating of the mixture. Other compounding ingredients well known and used in elastomer compounds can also be added. Solid additives include reinforcing agents, fillers, pigments, and resins. Examples of such materials are carbon black, silica, calcium carbonate, titanium dioxide, hydrocarbon resins, and phenolic resins. Liquid additives include processing oils, plasticizers, both monomeric and polymeric, and liquid nitrile rubber.
Other materials such as stabilizers, antioxidants, antiozonants, lubricants, release agents, and additives that improve certain properties of the compound can be added in minor proportions.
Vulcanization of the blends is accomplished by known means. The chemical vulcanizing agents can be added in a Banbury mixer, a roll mill, or other mixing device under conditions which avoid premature curing of the compound > While co-curing of the butadienejacrylonitrile polymer and the ethylene/carbon monoxide or sulfur dioxide copolymer ingredient of this composition may give superior properties, it is not an essential part of this invention.
Chemical agents usually employed for vulcanization of butadiene/acrylonitrile polymers are satisfactory for curing the blends of the present invention.
Acceleration of vulcanization and a variety of curing systems for nitrile rubber are discussed in Chapters 5 and 6, respectively, of "Vulcanization of Elastomers", edited by G. Alliger and I. J. Sjothun (Reinhold Pubiishing Corporation), and in trade literature. Trade literature from B. F. Goodrich Chemical Company on this subject includes: Manual HM-7, revised (601 1-6710-LP), "Accelerators, Pigments, and Plasticizers for Hycar Nitrile Rubber"; Manual HM-9, revised (6906-SPM), "Vulcanizing Nitrile Rubber," the disclosure of the above publications is hereby incorporated by reference.
Typical curing agents are peroxides and suifur/accelerator systems. Organic accelerators can be, and generally are, used in combination with the vulcanizing agent and dispersed throughout the vulcanizable blend in order to shorten the vulcanization times and lower curing temperatures. Further, the proportion of vulcanizing agent can be reduced. Any conventional accelerator can be used in the present invention. Representative accelerators that can be used alone or in admixture include the thiazoles, mercapto accelerators such as mercaptobenzothiazole, and sulphenamide accelerators, e.g., derivatives of mercaptobenzothiazole; guanidine accelerators, e.g., diphenylguanidine (DPG) and di-otolylguanidine (DOTG); thiurams, such as thiuram monosulfides and thiuram disulfides; and dithiocarbamates.The amount of accelerator used can vary over a wide range and the amount depends on the particular chemical composition, the accelerator and the intended use of the elastomer.
Generally, the amount of accelerator used will be from about 0.2 to 4, preferably 0.5 to 2, parts per 100 parts of nitrile rubber. In addition accelerator activator systems containing zinc oxide and stearic acid can also be used.
The final composition is shaped by known means, such as extrusion, injection molding, compression molding, transfer molding, or calendering into a sheet or onto a substrate, and cured.
Steam, hot fluid, or microwave heating can be used for their curing generally at temperatures from about 1000C to 21 00C for about 0.5 to 120 minutes.
The following examples are given for the purpose of illustrating the present invention. All parts and percentages are by weight unless otherwise specified.
EXAMPLES 1-2 These examples illustrate sulfur and peroxide cures of E/VA/CO-nitrile rubber vulcanizates using carbon black reinforcement, different nitrile rubbers, and different ethylene/vinyl acetate/carbon monoxide terpolymers. The compositions and the properties are summarized in Table These compounds were mixed on a 3" x 7" mill, sheeted off, and press cured at 1540C for 30 minutes. Tensile properties were determined on an Instron Tensile Tester.
A control composition, containing no modifier is shown below in Control Example C1.
Compared with the unmodified nitrile rubber compound of Example C1 below, the compositions of these Examples exhibit improved milling behavior; that is, formation of a smoother bank in the roll mill and more ready incorporation of the carbon black.
As is well known in the art, the behavior of a compound on a roll mill is an important'prncessing parameter. Formation and maintenance of a smooth bank and a continuous band assist in incorporation of other ingredients of the compound. When the ethylene copolymers of this invention are added to nitrile rubber which is being milled, the band is maintained. In contrast, when liquid softeners of the prior art are added, such as the polyester used in Control Example C3, the band is frequently disrupted until the liquid is absorbed.
TABLE I E/X/CO-Nitrile Rubber Vulcanizates Ingredients, phr(4) Ex. 1 Ex. 2 Ex. 3 "Hycar" 1041 (1) 100 - - "Hycar" 1042(2) - 100 100 "Hycar" 1 043' E/23.5% VA/1 1% CO Copolymer, 35 Ml 30 E/29% VA/10% CO Copolymer, 35 Ml 30 E/25.5% MA/8.6% CO Copolymer, 6 Ml - - 30 Zinc Oxide 5 5 5 Sulfur 1.5 SRF Carbon Black 60 60 60 Stearic Acid 1.0 1.0 1.5 Mercaptobenzothiazyl Sulfide 1.5 Dicumyl Peroxide/CaCO3 (40/60) ---- 4.0 4.0 Tensile Properties Tensile Strength, MPa 13.7 13.6 15.0 Elongation, % 390 470 430 Modulus @; 100% Elong., MPa 3.6 1.9 2.3 Shore A Hardness, Points 76 61 65 i butadiene/acrylonitrile polymer (nitrile rubber), available from B. F. Goodrich Company, containing 41% acrylonitrile (AN), and having a Mooney viscosity of 80 (2)33% AN, 80 Mooney 3)29% AN, 80 Mooney (4)parts per hundred parts of rubber ingredient EXAMPLE 3 In this example the ethylene copolymer used was E/25.5% methyl acrylate/8.6% CO, 6 Ml, and the nitrile rubber employed was "Hycar" 1042, 33% acrylonitrile, 80 Mooney viscosity. The remaining ingredients were the same as in Example 2. Stearic acid was increased from 1.0 phr to 1.5. Milling was carried out on a 6" x 15" mill. Sheeted samples were compression molded and cured at 1 540C for 30 minutes.The composition and the properties are summarized in Table I. Following air oven aging for 70 hours at 121 C, tensile strength, elongation, modulus at 100% elongation and Shore A hardness values were, respectively, 17.0 MPa, 360%, 3.4 MPa, and 69.
Comparison properties for the unmodified "Hycar" 1042 vulcanizate are shown in Control Example C1,Table I.
As with Example 2, modification with the E/MA/CO polymer gave improved milling behavior of the compound and softened the vulcanizate.
Control Examples C1-C3 and Examples 4-5 These examples compare properties of black-reinforced nitrile rubber compounds containing: (C1) no added plasticizer, (C2) and E/VA copolymer combined with a monomeric phthalate plasticizer (4) an EAfA/CO copolymer with the phthalate plasticizer, (C3) a polymeric polyester plasticizer, and (5) E/VA/CO copolymerwith polymeric plasticizer. These compounds were processed in a manner identical to that described in Example 3. The composition and properties of the compounds are shown in Table II.
The properties were determined in accordance with the ASTM procedure specified. It should be noted that data on the solvent-exposed samples are the "immediate deteriorated" properties, that is, tested with solvent still saturating the sample. Examples 4 and 5 are embodiments of the present invention.
Example 4 is a preferred embodiment because it combines good performance at moderate cost. Both the E/VA-modified compound of Example C2 and the E/VA/CO-modified compound of Example 4 provide superior low temperature properties in Clash-Berg stiffness and low temperature brittleness compared with the other compounds in this series. In addition, however, the compound of Example 4 is superior to that of Example C2 in resistance to oven aging and exposure to soivents, as shown by the reduced percentage change in properties. The reduced volume swell following exposure to Reference Fuel "B" is noteworthy. The compound of Example 4 is lower in cost than the compound of Example C3, while giving, on balance, equal or better properties.The compound of Example 5 offers somewhat higher initial tensile strength than does the compound of Example 4 but does not offer any improvement in aged properties.
TABLE II Comparison of Nitrile Rubber Vulcanizates Containing Different Softeners INGREDIENTS, phr Ex. C1 Ex. C2 Vex. 4 Ex. C3 Ex. 5 "Hycar" 1042 100 100 100 100 100 E/23.5% VA/1 1% CO, 35 MI Copolymer - - 15 - 15 E/40% VA, 57 Ml Copolymer - 15 "Santicizer" 711(1) 15 15 "Santicizer" 429(-2) - - - 30 15 SRF Black 60 60 60 60 60 Zinc Oxide 5 5 5 5 5 Stearic Acid 1.5 1.5 1.5 1.5 1.5 Dicumyl Peroxide/CaCO3 (40/60) 5 5 5 5 5 PHYSICAL PROPERTIES Original Cured 30 Min. @ 1 550C Tensiie Strength (ASTM D 471), MPa 19.0 14.0 14.3 17.2 16.9 Elongation, % 230 440 360 400 380 Modulus & ommat; 100% Elong., MPa 4.5 1.9 2.1 1.5 2.4 Shore A Hardness, points (ASTM D 2240) 70 57 61 50 60 Compress. Set (ASTM D 395, B), % 23 27 39 23 35 TABLE II (cont.) PHYSICAL PROPERTIES (cont.) Ex. C1 Ex. C2 Ex. 4 Ex. C3 Ex.
Mooney Scorch (ASTM D 121 C MV, Units 42 17 22 16 23 #5, Min. 18 30 70 30 30 A35, Min. 45 Clash-Berg (ASTM D 1043) Tf 10,000, C -23 -34 -34 -33 -30 Brittle Point (ASTM D 746), C -42 -45 -45 -41 -40 Aged(3) Air Oven 70 Hr. & ommat; 121 C (ASTM D 573) Tensile Strength, MPa 20.3 15.2 16.3 16.1 16.1 (+6) (+8) (+14) (-6) (-5) Elongation, % 200 330 280 300 240 (-13) (-25) (-22) (-25) (-37) Modulus @ 100% Elong., MPa 6.4 3.4 3.5 2.5 4.3 (+43) (+85) (+64) (+64) (+77) Shore A Hardness, points 76 67 65 51 68 (+6) (+10) (+4) (+1) (+8) (Pts) (Pts) (Pts) (Pts) (Pts) Ref.Fuel "B," 70 Hr. @ R.T. (ASTM D471 ? Tensile Strength, MPa 9.2 6.3 8.8 8.8 8.1 (-52) (-55) (-38) (-49) (-52) Elongation, % 150 200 220 220 190 (-35)' (-54) (-39) (-45) (-50) Modulus 100%Elong.,MPa 4.3 1.9 2.1 1.5 2.6 (-5) (+4) (-3) (0) (+6) Shore A Hardness, points 58 38 47 37 43 (-12) (-19) (-14) (-13) (-17) (Pts.) (Pts.) (Pts.) (Pts.) (Pts.) Volume Sweli, % +30 +46 +28 +32 +38 Methanol, 70 Hr. @ 640C (ASTM D 471) Tensile Strength, MPa 10.2 8.9 9.0 9.6 9.2 (-46) (-36) (-37) (-44) (-45) Elong., % 170 290 200 260 210 Modulus @; 100% Elong., MPa 3.6 1.8 3.0 1.5 2.7 (-18) (-4) (+39) (0) (+11) Shore A Hardness, pts. 63 45 48 44 53 (-7) (-12) (-13) (-6) (-7) (Pts.) (Pts.) (Pts.) (Pts.) (Pts.) TABLE II (cont.) Comparison of Nitrile Rubber Vulcanizates Containing Different Softeners PHYSICAL PROP. (cont.) Ex. C1 Ex. C2 Ex. 4 Ex. C3 Ex. 5 Volume Swell, % +19 +14 +12 +7 +14 11)Alkyl phthalate plasticizer, the alkyl group having 7-11 1 carbon atoms and about 30% branching, available from Monsanto Company.
2)Medium-high molecular weight polymeric polyester plasticizer, available from Monsanto Company.
(3)Change from original values is shown in parentheses. The change is expressed in percentages except where otherwise indicated.
EXAMPLES 6-7 These examples show nitrile rubbervulcanizates modified with different E/CO/softening comonomercopolymers. Example 6 utilizes an E/21%ethylhexyl acrylate/7.7%carbon monoxide copolymer having a melt index of 70. Example 7 utilizes E/20% methyl vinyl ether 1% carbon monoxide polymer having a melt index of 40. As shown by the tensile data in Table Ill, these sulfurcured vulcanizates possessed very good properties.
TABLE Ill VCO/X--Nitrile Rubber Vulcanizates Ingredient, phr Ex. 6 Ex. 7 "Hycar" 1042 100 100 E/21% EHA/7.7% CO, 70 Ml 15 E/20% MVE/11% CO,40 Ml - 15 "Santicizer" 711 15 15 SRF Black 60 60 Zinc Oxide 5 5 Stearic Acid 1 1 Sulfur 1.5 1.5 Mercaptobenzothiazyl Sulfide 1.5 1.5 Di-Orthotolyl Guanidine 2 2 Physical Properties Samples Cured 30 Min.
@ 1 550C Tensile Strength, MPa 16.8 14.6 Elongation, % 500 440 Modulus @ 1 00% Elong., MPa 2.9 2.6 Shore A Hardness, Points 64 62 EXAMPLE 8 This example shows the use of an ethylene copolymer to modify a prefluxed blend of 70% nitrile rubber and 30% "Geon" polyvinyl chloride resin, sold commercially under the trade name of "Hycar" 1203 by the B. F. Goodrich Chemical Company.A mill batch was made which contained in parts by weight: 100 of "Hycar" 1203; 20 of an E/23.5% VA/1 1% CO copolymer having a melt index of 35; 20 of "Santicizer" 711 phthalate plasticizer; 60 of SRF carbon black, 3.5 of zinc oxide; 1 of stearic acid; and 4 of dicumyl peroxide/calcium carbonate carrier (40% peroxide/60% calcium carbonate, available commercially as "Luperox" 500 40C from Lucidol Division of Pennwalt Corporation). The original vulcanizate properties following curing at 1 550C for 30 minutes were as follows: tensile strength, 14.5 MPa; elongation, 3109/0; modulus at 100% elongation, 5.1 MPa; Shore A hardness 73; Clash-Berg Tf 10,000, 200 C.
EXAMPLE 9 This example shows the use of 1 5 parts by weight each of E/24% MA/9.7% CO, 6 MI polymer, "Santicizer" 711 phthalate plasticizer, and "Nevex" 100 hydrocarbon resin (sold by Neville Chemical Company), 100 parts of "Hycar" 1042 nitrile rubber, 60 parts of SRF Black, 5 parts of zinc oxide, 1.5 parts of stearic acid, and 4 parts of dicumyl peroxide/calcium carbonate carrier (40% peroxide/60% calcium carbonate). The warm composition prior to vulcanization was soft and tacky. It is known in the art that unmodified nitrile rubber compounds are relatively stiff and boardy. By use of the combination of the E/X/CO or SO2 polymer with phthalate plasticizer and even more so with these two modifiers plus hydrocarbon resin, the nitrile rubber compound is rendered more pliable.This property allows the compound to conform better to surfaces and is thus helpful when building up objects having several layers such as fabric-reinforced hose. Following press curing at 1 550C for 30 minutes, the vulcanizate properties were: tensile strength, 10.3 MPa; elongation, 710%; modulus at 100% elongation, 1.2 MPa; Shore A hardness, 51; Clash-Berg Tf 10,000, -300C; and brittleness temperature, -340C. After air oven aging 70 hours at 121 C, the tensile property values were, respectively, 13.8 MPA, 500%, 1.9 MPa; and the compound increased 7 points to a hardness of 58.
EXAMPLES 10-11 Two other nitrile rubber compounds were made up in a manner identical to that shown in Example 6, except for the substitution of an E/29% VA/9% S 2 copolymer having an MI of 60 (Example 10) or an E/1 1%AN/12% CO copolymer having an Ml of 0.2 (Example 11). The vulcanizate properties, original and after oven aging, are shown in Table IV.
TABLE IV E/CO or SO2/X-Nitrile Rubber Vulcanizate Properties Original Ex.10 Ex.11 Tensile strength, MPa 14.6 14.4 % Elongation 390 570 Modulus at 1009/0 Stress, MPa 3.0 2.0 Shore A Hardness, points 67 63 Aged 70 Hours at 1210C Tensile Strength, MPa 16.4 17.3 % Elongation 340 360 Modulus at 100% Stress, MPa 4.3 3.9 Shore A Hardness, points 71 72 CONTROL EXAMPLE C4 AND EXAMPLE 12 These examples show the effect of E/23.5% VA/1 1% CO, 35 Ml copolymer as a hardness-reducing modifier for nitrile rubber reinforced with cashew nut oil-modified phenolic resin containing 8% hexamethylene tetramine, available commercially from Hooker Chemical Co. as "Durez" 12687 resin. In Control Example C4, a compound was prepared by milling 100 parts of 33% nitrile content, 80 Mooney nitrile rubber, 60 parts of the phenolic resin, 5 parts of zinc oxide, 1.5 parts of stearic acid, 1.5 parts of sulfur, and 1.5 parts of mercaptobenzothiazyl sulfide. Example 12 contained in addition 30 parts of the above E/VA/CO copolymer. Slabs were press-cured at 1 C for 30 minutes. Table V shows tensile and hardness properties of the vulcanizates after curing and after aging 70 hours at 121 OC.
TABLE V Nitrile Rubber-Phenolic Vulcanizates Original Properties Ex. C4 Ex. 1 2 Tensile Strength, MPa 19.0 1 5.5 % Elongation 200 230 Modulus at 100% Stress, MPa 14.8 7.5 Shore A Hardness, points 95 84 Aged 70 Hoursat1210C Tensile Strength, MPa 21.9 12.3 % Elongation 75 100 Modulus at 1 00% Stress, MPa ---- 12.5 Shore A Hardness, points 97 86 The properties of the vulcanizate of Example 12 show that the E/VA/CO polymer has reduced considerably the modulus and hardness of the original vulcanizate. Following air oven aging, the E/VA/CO-modified vulcanizate has maintained 100% elongation, while the unmodified vulcanizate has only 75% elongation.

Claims (6)

CLAIMS:
1. A curable blend of ethylene terpolymer and butadiene/acrylonitrile polymer characterized in that said blend (a) 100 parts of a butadiene/acrylonitrile polymer containing about 2050 weight percent of acrylonitrile and (b) about 3-100 parts of ethylene copolymer selected from the group consisting of ethylene/carbon monoxide/X and ethylene/sulfur dioxide/X copolymers, wherein comonomer X is (I) a vinyl ester of an alkanoic acid, the acid having 1 to 18 C atoms, (II) an alkyl acrylate or methacrylate, the alkyl group having 1 to 18 C atoms, (III) alkyl vinyl ether, the alkyl group having 1 to 4 C atoms, (IV) acrylonitrile or methacrylonitrile, or combinations of the above comonomers, the ethylene copolymer containing about 3-25 weight percent of carbon monoxide or sulfur dioxide, about 10--65 weight percent of comonomer X, and about 30-75 weight percent of ethylene.
2. A composition comprising a blend of Claim 1, and a peroxide or sulfur curing system.
3. A vulcanized product obtained by heating the composition of Claim 2 for about 0.5-120 minutes at about 1 000 C--21 OOC.
4. A curable blend in accordance with Claim 1 substantially as hereinbefore described in any one of the Examples.
5. A composition in accordance with Claim 2 substantially as hereinbefore described in any one of the Examples.
6. A vulcanized product in accordance with Claim 3 substantially as hereinbefore described in any one of the Examples.
GB7929733A 1978-08-29 1979-08-28 Curable blends of butadiene/acrylonitrile polymer and ethylene copolymer Expired GB2028837B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4329278A (en) 1981-03-11 1982-05-11 E. I. Du Pont De Nemours And Company Molding compositions
US4329276A (en) 1981-03-11 1982-05-11 E. I. Du Pont De Nemours And Company Molding components
US4591615A (en) * 1984-02-28 1986-05-27 The British Petroleum Company P.L.C. Thermoplastic elastomer composition
US4725637A (en) * 1985-04-24 1988-02-16 Bp Chemicals Limited Process for the production of a thermoplastic elastomer composition
EP0384210A1 (en) * 1989-02-20 1990-08-29 Bayer Ag Cross-linkable blends based on hydrogenated nitrile rubber and an ethylene/CO copolymer
CN103589008A (en) * 2013-10-15 2014-02-19 广东奥美格传导科技股份有限公司 Irradiation-crosslinked wear-resistant oil-resistant cable

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63137939A (en) * 1986-11-28 1988-06-09 Nitta Kk Rubber composition for belt and made thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3684778A (en) * 1970-04-28 1972-08-15 Du Pont Polymers of ethylene, sulfur dioxide and ethylenic monomers
US3780140A (en) * 1971-08-06 1973-12-18 Du Pont Ethylene/carbon monoxide polymer compositions
AR204831A1 (en) * 1973-05-08 1976-03-05 Du Pont SUITABLE CURABLE BLENDS TO BE USED IN VULCANIZABLE COMPOSITIONS VULCANIZABLE COMPOSITIONS AND VULCANIZED PRODUCTS
US3873494A (en) * 1973-05-08 1975-03-25 Du Pont Oil-resistant and aging-resistant elastomers

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4329278A (en) 1981-03-11 1982-05-11 E. I. Du Pont De Nemours And Company Molding compositions
US4329276A (en) 1981-03-11 1982-05-11 E. I. Du Pont De Nemours And Company Molding components
US4591615A (en) * 1984-02-28 1986-05-27 The British Petroleum Company P.L.C. Thermoplastic elastomer composition
US4725637A (en) * 1985-04-24 1988-02-16 Bp Chemicals Limited Process for the production of a thermoplastic elastomer composition
EP0384210A1 (en) * 1989-02-20 1990-08-29 Bayer Ag Cross-linkable blends based on hydrogenated nitrile rubber and an ethylene/CO copolymer
CN103589008A (en) * 2013-10-15 2014-02-19 广东奥美格传导科技股份有限公司 Irradiation-crosslinked wear-resistant oil-resistant cable

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IT7925320A0 (en) 1979-08-28
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CA1136318A (en) 1982-11-23
DE2934931A1 (en) 1980-03-13
FR2434836A1 (en) 1980-03-28
BE878473A (en) 1980-02-28
JPS5531892A (en) 1980-03-06
NL7906468A (en) 1980-03-04
IT1122521B (en) 1986-04-23

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