US20060270783A1

US20060270783A1 - Elastomer compositions for use in a hydrocarbon resistant hose

Info

Publication number: US20060270783A1
Application number: US11/493,722
Authority: US
Inventors: Harold Beck
Original assignee: Dayco Products LLC
Current assignee: Yokohama Industries Americas Inc
Priority date: 2003-09-15
Filing date: 2006-07-26
Publication date: 2006-11-30

Abstract

A heat tolerant, pressure resistant elastomeric composition comprising a blend of a first ethylene-vinyl ester copolymer and a second copolymer selected from the group consisting of chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polychloroprene (CR), ethylene-acrylic elastomer (AEM), alkyl-acrylate copolymer (ACM), polyvinyl acetate (PVA), nitrile-butadiene rubber (NBR), hydrogenated nitrile-butadiene rubber (HNBR), and mixtures thereof; a hose manufactured therefrom; and a method for preparing the hose are described.

Description

This application is a continuation-in-part of U.S. patent application Ser. No. 10/830,790, filed Apr. 21, 2004, which is a continuation-in-part of U.S. patent application Ser. No. 10/663,324 filed Sep. 15, 2003.

BACKGROUND OF THE INVENTION

The present invention relates generally to polymeric compositions. More particularly, the present invention relates to polymeric compositions useful in the manufacture of automotive components, particularly automotive hoses for the transport of automotive fluids.
Hoses, particularly rubber hoses, are used in a variety of applications in the automotive industry as fuel feed hoses, torque converter hoses, power steering hoses and air conditioner hoses; as well as for industrial and household utility applications such as hydraulic hoses, refrigeration hoses, washing machine hoses, propane gas feed hoses, high pressure air hoses, garden hoses, etc.
It is generally known that rubber surfaces do not always exhibit desired resistance against chemical loads such as organic gases and solvents. Therefore, other approaches for improving the organic gas and solvent resistance of rubber materials included using rubber materials which have a different polarity than the organic gas or solvent, increasing the crosslinking of the rubber material, adding or increasing certain additives, and increasing the wall thickness of the rubber tube material. All of these approaches have a down side. For example, the use of a rubber material having a polarity different from the organic gas or solvent requires the use of more expensive rubber materials such as chloroprene rubber, acrylic rubber, epichlorohydrin rubber, and the like; increasing the degree of crosslinking of the rubber used detracts from the softness and flexibility of the rubber; the addition of additives affects the processability and certain physical properties of the rubber; and increasing the wall thickness of the rubber material also increases the weight of the structure. Generally, these undesirable effects overshadow any advantage gained in the improved gas and solvent resistance.
In order to improve the impermeability of multilayered rubber hoses, typical approaches include the use of a metal film as a barrier layer coated on one of the inner layers. Such disclosures appear, for example, in U.S. Pat. No. 318,458 to Fletcher where there is disclosed a multilane tubular structure made from India rubber and having a tin foil liner. Other prior art patents such as U.S. Pat. Nos. 4,559,793 to Hanes et al.; 4,759,455 to Campbell et al.; 5,182,147 to Davis; 5,271,977 to Yoshikawa et al; 5,360,037 to Lindstrom; 5,398,729 to Spurgat; and 5,476,121 to Yoshikawa et al. have attempted similar methods to reduce the permeability of fluids and/or gases through various tubes. Commonly assigned U.S. Pat. No. 6,074,717 to Little et al.; and U.S. Pat. Nos. 4,779,673 and 5,488,975 to Chiles et al. disclose metal coated synthetic rubber hoses used for circulation of fluids in radiant heating systems in houses and in businesses and disclose the use of an inner nylon tubular layer having a metal layer surrounding the nylon layer.
Polymeric material used to form the hose for accommodating fluids and gases under elevated pressures and/or high temperatures such as in automotive air conditioner cooler hoses and power steering hoses must meet other critical requirements. For example, the polymeric material must exhibit low permeability to FREON or other coolant gases to prevent such gases from escaping from the hose. Also such polymeric hose must be able to prevent outside moisture from entering the interior of the hose where it could contaminate the fluid or gas. In addition, the polymeric hose must be capable of withstanding high heat and pressure, be able to withstand engine and impact vibration, and be capable of forming gas-tight connections.
In the case of hoses for accommodating coolant fluid for automotive air conditioners, etc., polymeric materials such as polychloroprene (CR), acrylonitrile-butadiene rubber (NBR), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polyacrylate (PA), ethylene-acrylic rubber (AEM), alkyl acrylate copolymer (ACM), polyvinyl acetate, acrylonitrile-butadiene rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (HNBR), ethylene-propylene-diene terpolymer (EPDM), cis-polybutadiene, cis-polyisoprene, polyurethane, polyamides such as nylon are often used as the material for forming the hose. For example, nylon 6 and nylon 66 are very low in coolant gas permeability, but are relatively high in moisture permeability. On the other hand, nylon 11 and 12 are relatively low in moisture permeability and less susceptible to hydrolysis, but are moderately high in gas permeability. Blends of any of the various nylons with other nylons, olefins or other materials are also used in such applications. For example, blends such as nylon 6, nylon 4, nylon 66, nylon 11, nylon 12, have been made to take advantage of desirable characteristics of one or more of such nylons and, at the same time, reduce the effects of any undesirable characteristics. However, blending the various polymeric materials for the purpose of obtaining the desired benefits of each individual component actually acts to reduce the desired benefit because of the dilution effect of the other component(s) employed. Therefore, while one can obtain a variety of benefits by blending various polymers, the actual observed benefits may be reduced.
Ethylene-vinyl acetate copolymer (VAE) compositions are known. For example, U.S. U.S. Pat. Nos. 4,338,227 6,492,454; 5,942,580; 5,837,791; 5,830,941; 5,807,948; 5,744,566; 5,698,651; 5,362,533; 5,135,988; 4,338,227 and 4,309,332 describe various ethylene-vinyl acetate copolymers and the uses thereof. Copolymers of ethylene and vinyl acetate exhibit elastomeric characteristics and are commonly used to improve adhesion properties of hot melt, solvent-based and pressure-sensitive adhesives. It is generally well known that the use of ethylene-vinyl acetate copolymers in the automotive industry and commercial applications are mostly limited to coatings, adhesives, gaskets, O-rings and the like. For example, “Ultrathene”, a series of ethylene-vinyl acetate copolymers manufactured by Quantum Chemical, is typically used for adhesives, conversion coatings and thermoplastic modifiers. Such EVA copolymers exhibit a wide range of melt indexes. Ethylene-vinyl acetate copolymers are also marketed by Bayer under the trade name “Levapren”. These EVA copolymers are described as oil and heat resistant materials which may be used in air hose applications. U.S. Pat. No. 6,605,327 to Ramey et al. teaches the use of two separate layers of an ethylene-vinyl copolymer in the manufacture of a multilayer hose.
Blends of vinyl esters with other polymers have been found to be somewhat effective in the manufacture of automotive hoses. For example, blends of ethylene-vinyl acetate with ethylene-vinyl acetate-carbon monoxide terpolymers are useful in applications were flame retardant, low smoke, oil resistant flexible systems are desirable as coatings such as coatings for wire and cable construction, are described in U.S. Pat. No. 6,133,367 to Arhart. However, there is no mention in the prior art of blends of a first vinyl ester with second copolymer selected from the group consisting of chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polychloroprene (CR), acrylonitrile-butadiene rubber (NBR), polyacrylate (PA), ethylene-acrylic rubber (AEM), alkyl acrylate copolymer (ACM), polyvinyl acetate, acrylonitrile-butadiene rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (HNBR), ethylene-propylene-diene terpolymer (EPDM), cis-polybutadiene, cis-polyisoprene.
Ethylene-vinyl acetate copolymers and blends thereof have been employed in the wire and cable industry as a sheath or cover material surrounding electrical wires. For example, polymeric blends of ethylene-vinyl acetate copolymers with ethylene-vinyl acetate-carbon monoxide terpolymers which are particularly useful in applications where flame retardant, low smoke, oil resistant, flexible systems are desirable as a wire coating. Patents disclosing the use of ethylene-vinyl acetate copolymers as wire and cable coatings include U.S. Pat. No. 4,349,605 to Biggs et al.; U.S. Pat. No. 4,381,326 to Biggs et al; U.S. Pat. No. 4,477,523 to Biggs et al.; U.S. Pat. No. 5,191,004 to Maringer et al.; U.S. Pat. No. 5,225,460 to Maringer et al.; and U.S. Pat. No. 5,226,489 to Maringer et al. None of the references describe a self supporting tubular structure, nor is there any teaching of a blend of a first vinyl ester and a second copolymer selected from the group consisting of polychloroprene (CR), acrylonitrile-butadiene rubber (NBR), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polyacrylate (PA), ethylene-acrylic rubber (AEM), alkyl acrylate copolymer (ACM), polyvinyl acetate, hydrogenated acrylonitrile-butadiene rubber (HNBR), ethylene-propylene-diene terpolymer (EPDM), cis-polybutadiene, cis-polyisoprene.
Choosing the right material or combination of materials to be used in the construction of automotive hoses is becoming more and more difficult because the hoses are now required to withstand higher pressures and temperatures than previous hoses performing the same tasks. Also mandated regulations require that the hoses exhibit greater impermeability rates and resist stress over longer periods of time while maintaining manufacturing costs at an acceptable level. Therefore, the manufacturers of automotive hoses find it necessary to come up with newer and better materials and combinations of materials to meet these rising needs. In order to achieve a material which meets regulations and still retains the many desirable characteristics necessary to satisfy the manufacturer, attempts have been made to blend various materials which individually exhibit the desirable characteristics. However, it is generally found that, while these blended composite materials may exhibit all of the desirable characteristics, these desirable characteristics have been drastically diluted to the point where the material is no longer acceptable.
Accordingly, in the manufacture of automotive components, particularly hoses for use in the automotive industry, it would be desirable to find a material blended from two or more individual polymers, each of which exhibits one or more desirable characteristics, wherein the individual characteristics in the resulting blend are not diluted by the other polymers.

SUMMARY OF THE INVENTION

It has now been found that blends of certain copolymers containing a vinyl ester and at least one other polymer selected from the group consisting of ethylene-acrylic elastomer (AEM) or an alkyl-acrylate copolymer (ACM) or mixtures thereof, exhibit unexpected properties that are desirable in the manufacture of a variety of industrial and automotive rubber components, such as automotive hoses, transmission belts, seals, dampers, engine mounts, particularly oil filled engine mounts, air duct housing, gaskets, CV joints boots, etc. For example, such blends exhibit high temperature and pressure resistance, improved tensile strength, and improved hydrocarbon fluid resistance over either of the individual components alone. The particular copolymer blends of the present invention have been found to be particularly effective in forming hoses useful in the transmission of various automotive fluids and gases, e.g., engine oil cooler fluids, transmission oil cooler fluids, power steering fluids, radiator fluids, heater fluids, and the like. For example, blends containing a first vinyl ester of a C₂to C₆carboxylic acid, e.g., vinyl acetate, and a second polymer such as an ethylene-acrylic elastomer (AEM) or an alkyl-acrylate copolymer (ACM) or mixtures thereof not only exhibit high temperature and pressure resistance, tensile strength, and improved hydrocarbon fluid resistance, but such blends appear to preserve the individual characteristics of each of the copolymer components of the blend.
Typically, ethylene-vinyl acetate copolymers are known to be heat resistant elastomers which are only fairly resistant to common fluids such as transmission fluids and power steering fluids. In order to improve the oil resistance of an ethylene-vinyl acetate copolymer material, one approach would be to blend an oil resistant polymer with the ethylene-vinyl acetate copolymer. Some of the more common oil resistant polymers would include chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polychloroprene (CR), polyvinyl acetate (PVA), nitrile-butadiene rubber (NBR), hydrogenated nitrile-butadiene rubber (HNBR), and the like. However, the blending of two ore more of these materials to obtain the beneficial characteristics of each material, more often than not, is only marginally successful, because the blending of the two materials simply dilutes their characteristics in the blend as compared to the individual components alone. The diluted characteristics of the blended material generally are most apparent when the material is aged.
It has now been discovered that blends of an ethylene-vinyl ester, e.g., vinyl acetate, with certain other polymers, particularly, ethylene-acrylic elastomers (AEM) or alkyl-acrylate copolymer (ACM) or mixtures thereof, not only provide a material for use in the manufacture of hoses which meet government standards with regard to permeability rates, has good tensile strength, has good oil resistance, and has good heat and pressure resistance, but such blends, unexpectedly, do not show the typical effects of dilution. Such blends exhibit desirable characteristics which unexpectedly retain the desirable characteristic of the individual polymers when used alone. That is, the blend of polymers exhibits the beneficial properties of each polymer without the undesirable effects of dilution.
In one embodiment of the present invention, there is provided a heat tolerant, pressure and hydrocarbon resistant composition, which exhibits, improved hydrocarbon fluid impermeability. The heat tolerant, pressure and hydrocarbon resistant composition of the invention comprises a blend of a first copolymer and a second polymer wherein the first copolymer is different from the second polymer. The first copolymer comprises an ethylene-vinyl ester of a lower carboxylic acid and the second polymer is selected from the group consisting of ethylene acrylic elastomer (AEM) and alkyl-acrylate copolymer (ACM) or mixtures thereof. Other polymeric materials may be employed in place of, or in combination with, the ethylene-acrylic elastomer or alkyl acrylate copolymer; however, such other polymers when blended with ethylene-vinyl acetate are only marginally effective Most notably, these other polymers include chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polychloroprene (CR), ethylene-acrylic elastomer (AEM), alkyl-acrylate copolymer (ACM), polyvinyl acetate (PVA), nitrile-butadiene rubber (NBR), hydrogenated nitrile-butadiene rubber (HNBR), and the like.
In another embodiment of the present invention, there is provided a hose especially useful if the automotive industry to transport fuel, oil and various fluids. The hose of the present invention is manufactured from a blend of a first vinyl ester copolymer and a second copolymer selected from the group consisting of ethylene-acrylic elastomer (AEM), alkyl-acrylate copolymer (ACM), and mixtures thereof. As indicated above, other polymers such as chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polychloroprene (CR), polyvinyl acetate (PVA), nitrile-butadiene rubber (NBR), hydrogenated nitrile-butadiene rubber (HNBR), and the like may be employed in addition to or in place of the ethylene-acrylic elastomer or alkyl acrylate copolymer, but such other polymers are only marginally effective. Most preferably, the present invention is directed to a blend of ethylene-vinyl ester, such as vinyl acetate, and an ethylene acrylic elastomer or alkyl acrylate copolymer. The automotive components formed from such ethylene-vinyl ester copolymers blended with an ethylene-acrylic elastomer, alkyl acrylate, or mixture thereof, exhibits excellent oil resistance, fuel impermeability, temperature and pressure resistance, and tensile strength.
In still another embodiment of the present invention, there is provided a method for manufacturing the hose of the present invention which comprises providing a first vinyl ester copolymer, providing a second copolymer selected from the group consisting of chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polychloroprene (CR), ethylene-acrylic elastomer (AEM), alkyl-acrylate copolymer (ACM), polyvinyl acetate (PVA), nitrile-butadiene rubber (NBR), hydrogenated nitrile-butadiene rubber (HNBR), and the like, preferably, ethylene-acrylic elastomer or alkyl acrylate copolymer, blending the first vinyl ester with the second copolymer, forming a hose from said blend, and vulcanizing the hose.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with a first embodiment of the invention, a polymeric composition comprises a blend of a first vinyl ester copolymer and a second polymeric member. The first vinyl ester copolymer comprises a vinyl ester of a C₂to C₆lower aliphatic carboxylic acid. Preferably, the vinyl ester copolymer is an ethylene-vinyl acetate copolymer wherein the vinyl-acetate copolymer contains about 40 to 80 vinyl acetate. Vinyl-acetate copolymers commercially available from Bayer Corporation under the name Levapren has been found to be particularly satisfactory as the first vinyl ester copolymer of the blend used in manufacturing the hose of the present invention. The vinyl ester copolymer is blended with a second polymer selected from the group consisting of ethylene-acrylic elastomer (AEM), alkyl-acrylate copolymer (ACM), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polychloroprene (CR), polyvinyl acetate (PVA), nitrile-butadiene rubber (NBR), hydrogenated nitrile-butadiene rubber (HNBR), and the like polyvinyl acetate (PVA), nitrile-butadiene rubber (NBR), hydrogenated nitrile-butadiene rubber (HNBR), and the like. In a preferred aspect of the invention, the second copolymer is an ethylene-acrylic elastomer (AEM) or an alkyl-acrylate copolymer (ACM). Most preferably, the second copolymer is an ethylene-acrylic elastomer available from E. I. DuPont under the name Vamac.
Additional materials may also be employed as additives compounded into the copolymer composition for the purpose of providing desired characteristics of the composition. These additional materials include, for example, process aids; fillers; plasticizers; metal oxides or hydroxides; peroxides; coagents, and antioxidants. Other additives such as vulcanization accelerators commonly used in polymeric compositions for use in preparing hoses may be added in appropriate amounts to provide their desired effect.
Suitable processing aids includes stearic acid, stearates, polyethylene, amines, oils, organic esters, organic phosphate esters, mixed styrenated phenylene diamine and the like.
Suitable fillers include materials, such as carbon black, silicon dioxide, fumed silica, precipitated silica, diatomaceous earth, magnesium carbonate, magnesium silicate, aluminum silicate titanium dioxide, talc, mica, aluminum sulfate, calcium sulfate, graphite, wollastonite, molybdenum disulfide, clay, calcium carbonate and combinations thereof.
Suitable plasticizers include materials such as hydrocarbons, glycols, aldehydes, ethers, esters, ether-esters, and the like.
Suitable metal oxides and metal hydroxides include zinc oxide, zinc hydroxide, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, aluminum hydroxide, and the like.
Suitable peroxides include 2,5-dimethyl-2.5-di(t-butylperoxy)hexyne-3; 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; a,a′-bis-(t-butylperoxy)-p-diisopropylbenzene, dicumyl peroxide, di-t-butyl peroxide; 1,1-bis(t-butylperoxy)-3,3,3-trimethylcyclohexane; 2,4-dichlorobenzoyl peroxide; benzoyl peroxoide; p-chlorobenzoyl peroxide; 4,4-bis(t-butylperoxy) valerate; t-butylcumyl peroxide; di-t-amyl peroxide; t-butyl hydroperoxide and combinations thereof.
Suitable coagents include N,N′, m-Phenylenedimaleimide (HVA2) and other bismaleimides; triallyl cyanurate; tiallyl isocyanurate; diallyl terephthalate; 1,2-vinyl polybutadienes; di- and tri-functional methacrylates and diacrylates; and metal ion versions of these coagents.
Suitable antioxidants include phenols, hydrocinnamates, diphenylamines, hydroquinone, hydroquinolines, mercaptobenzimidazoles, and the like.
Typically, the heat tolerant, pressure resistant elastomeric composition of the present invention comprises a blend of a first ethylene-vinyl ester copolymer of a lower carboxylic acid and a second polymer selected from the group consisting of ethylene-acrylic elastomer (AEM), alkyl-acrylate copolymer (ACM), and mixtures thereof. In certain application, other polymeric materials such as chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polychloroprene (CR), polyvinyl acetate (PVA), nitrile-butadiene rubber (NBR), hydrogenated nitrile-butadiene rubber (HNBR), and mixtures thereof, may also be employed in place of or in combination with the blend of ethylene-vinyl ester and ethylene acrylate elastomer, alkyl acrylate, or mixtures thereof. Preferably, the composition comprises a blend of an ethylene-vinyl acetate copolymer and an ethylene-acrylic elastomer or an ethylene-alkyl copolymer, and most preferably, the composition comprises a blend of ethylene-vinyl acetate and an ethylene-acrylic elastomer.
In accordance with a one embodiment of the invention, the composition comprises: about 10 to 75% by weight of a blend containing about 10 to 90% by weight of an ethylene-vinyl acetate copolymer having about 40 to 80% vinyl acetate, and about 90 to 10% of an ethylene-acrylic elastomer, an alkyl acrylate copolymer, or mixture thereof; and a plurality of additives in an amount of about 25 to 75% by weight, wherein the plurality of additives is selected from the group consisting of process aids; fillers; plasticizers; metal oxides or hydroxides; peroxides; coagents, and antioxidants.
Preferably, the composition of the present invention comprises:
about 10 to 50% by weight of a blend of an ethylene-vinyl ester with a polymer selected from the group consisting of ethylene-acrylic elastomer, alkyl acrylate, or mixtures thereof; and
about 0.8 to 2% by weight process aids based upon the total weight of the composition, wherein said process aids are selected from the group consisting of stearic acid, stearates, polyethylene, amines, oils, organic esters, organic phosphate esters and combinations thereof;
about 20 to 60% by weight fillers based upon the total weight of the composition, wherein said fillers are selected from the group consisting of carbon black, silicon dioxide, fumed silica, precipitated silica, diatomaceous earth, magnesium carbonate, magnesium silicate, aluminum silicate titanium dioxide, talc, mica, aluminum sulfate, calcium sulfate, graphite, wollastonite, molybdenum disulfide, clay, calcium carbonate and combinations thereof;
about 3 to 15% by weight plasticizers based upon the total weight of the composition, wherein said plasticizers are selected from the group consisting of hydrocarbons, glycols, aldehydes, ethers, esters, ether-esters and combinations thereof;
about 0 to 10% by weight metal oxides and/or hydroxides based upon the total weight of the composition, wherein said metal oxide and/or hydroxides are selected from the group consisting of zinc oxide, zinc hydroxide, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, aluminum hydroxide and combinations thereof;
about 0.5 to 2% by weight peroxides based upon the total weight of the composition, wherein said peroxides are selected from the group consisting of 2,5-dimethyl-2,5-d(t-butylperoxy)hexyne-3; 2,5-dimethyl-2,5-di(t-butyperoxy)hexane; dicumyl peroxide; a,a′-bis-(t-butylperoxy)-p-diisopropylbenzene; di-t-butyl peroxide; benzoyl peroxide; p-chlorobenzoyl peroxide; 4,4-bis(t-butylperoxiy) valerate; and combinations thereof;
about 0 to 5% by weight coagents based upon the total weight of the composition, wherein said coagents are selected from the group consisting of maleimides, triallyl cyanurate, triallyl isocyanurate, diallyl terephthalate, 1,2-vinyl polybutadiene, di- and tri-functional methacrylates, diacrylates, metal ion versions thereof and combinations thereof; and
about 0 to 0.3% by weight antioxidants based upon the total weight of the composition, wherein said antioxidants are selected from the group consisting of phenols, hydrocinnamates, hydroquinones, hydroquinolines, diphenylamines, mercaptobenzimidazoles, and combinations thereof.
In accordance with a most preferred embodiment of the invention, the composition comprises:
about 10 to 50% by weight of a blend containing about 10 to 90% by weight vinyl acetate copolymer having about 40 to 80% by vinyl acetate and about 90 to 10% ethylene-acrylate elastomer;
about 0.2 to 0.7% by weight stearic acid;
about 23 to 38% by weight carbon black;
about 2 to 5% by weight silicon dioxide;
about 3 to 7% by weight trioctyl trimellitate;
about 0 to 7% by weight adipate type plasticizer;
about 0 to 8% by weight magnesium oxide;
about 0.1 to 0.75% by weight 1-octanedecanamine;
about 0.1 to 0.75% weight organic phosphate ester;
about 0.5 to 4% by weight organic peroxide;
about 0.25 to 1% by weight triallyl cyanurate;
about 0.25 to 1% by weight N,N′, n-phenylenedimaleimide;
about 0.25 to 2% by weight antioxidant selected from the group consisting of phenols, hydrocinnamates, diphenylamines, hydroquinones, hydroquinolines and mixtures thereof.
The composition of the invention is particularly advantageous in the manufacture of tubular structures for use in the automotive industry, for example, for transporting fuel and other automotive fluids such as those fluids useful in engine oil coolers, transmission oil coolers, power transmission coolers, radiators, heaters, etc.
Hoses manufactured from the composition of the present invention not only exhibit good heat tolerance, pressure resistance and hydrocarbon impermeability, but such hoses unexpectedly retain such desired heat tolerance, pressure resistance, and hydrocarbon impermeability characteristics at a surprising effective level over long periods of time, even after aging.
In a third embodiment of the invention, a method for manufacturing heat tolerant, pressure and hydrocarbon resistant automotive components, such as automotive hoses having improved hydrocarbon fluid resistance is provided. The method includes
providing an elastomeric composition comprising a first copolymer and a second copolymer wherein said first copolymer is different from said second copolymer, said first copolymer is an ethylene-vinyl ester of a C₂to C₆lower carboxylic acid and a said second polymer comprises a copolymer selected from the group consisting of ethylene-acrylic elastomer (AEM), alkyl-acrylate copolymer (ACM) or mixtures thereof. Other polymers may be employed in addition to or in place of the of ethylene-acrylic elastomer (AEM), alkyl-acrylate copolymer (ACM) or mixtures thereof. Such polymers include chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polychloroprene (CR), polyvinyl acetate (PVA), nitrile-butadiene rubber (NBR), hydrogenated nitrile-butadiene rubber (HNBR), and mixtures thereof; incorporating into said elastomeric composition, one or more additives selected from the group consisting of process aids, fillers, plasticizers, metal oxides, metal hydroxides, peroxides, coagents, antioxidants and combinations thereof;
forming a hose of the blend containing the additives; and
vulcanizing the hose in an autoclave.
In a preferred method for manufacturing the tubular structure of the invention, a continuous spiral production method is employed which comprises providing an inner layer of a material produced in a mono-extrusion of an annular configuration.
A reinforcement material is generally employed in the manufacture of the hose to provide strength to the hose structure. The reinforcement materials include natural fibers such as cotton; synthetic fibers such as polyester, nylon, rayon, aramid; and metal wire. The reinforcement may be applied by knit or maypole type braid methods. Typically, the reinforcement material is applied to the annular extrudate in a two-layer spiral format in which one layer is applied in a clockwise direction and the other layer is applied in a counter-clockwise direction.
An outer protective cover layer may be employed over the reinforcement layer in a mono-extrusion of an annular configuration to provide to protect the hose from the outer environment. The cover layer is a protective layer of any of the commercially recognized materials for such use, e.g., elastomers, thermoplastic polymers, thermosetting polymers and the like. Typically, the protective cover is a synthetic elastomer having good heat resistance, oil resistance, weather resistance and flame resistance. Preferably, the outer protective cover layer is a synthetic elastomer selected from the group consisting of styrene-butadiene rubber; butadiene-nitrile rubber such as butadiene-acrylonitrile rubber; chlorinated rubber; chlorosulfonated polyethylene; vinylethylene-acrylic rubber; acrylic rubber; epichlorohydrin rubber such as Hydrin 200, a copolymer of epichlorohydrin and ethylene oxide available from DuPont ECO; polychloroprene rubber; polyvinyl chloride; ethylene-propylene copolymers; ethylene-propylene-diene terpolymers; ultra high molecular weight polyethylene; high density polyethylene; and blends thereof.
The hose of the invention is particularly useful in the transportation of air conditioner fluids, power steering fluids, transmission oil cooler fluids, etc. where the material forming the hose exhibits the required heat tolerance, pressure resistance, impermeability resistance to the fluid being transported through the hose, etc.

EXAMPLES

Example 1



	Parts per hundred of polymer (phr)

Levapren ® 500 HV	100	80	90	90
Hypalon ® 4085 (CSM)		10	10
Tyrin ® CM0136 (CPE)		10		10
Stearic Acid	1	1	1	1
Magnesium Oxide	10	10	10	10
N650 Carbon Black	75	75	75	75
Silicon Dioxide	5	5	5	5
Trioctyl Trimellitate	10	10	10	10
1-Octadecanamine	1	1	1	1
Triallyl Cyanurate, 72% Dispersion	1	1	1	1
N,N′-m-Phenylene Dimaleimide	1	1	1	1
Dicumyl Peroxide; 60% Active	4	4	4	4
4,4′-Di(methylbenzyl)diphenylamine	2	2	2	2
Polyethylene	2	2	2	2
Polyethylene Glycol	2	2	2	2
Cured 20 minutes @ 175° C.
Original Properties
Tensile Strength; psi	1699	2083	2059	1873
Elongation %	242	195	213	243
100% Modulus; psi	785	1187	1074	923
Hardness; Shore A	77	79	79	79
Compression Set, 70 h. @ 175° C.	48	73	58	51
After 336 hours @ 175° C. in Air
Tensile Strength; psi	1497	1993	2514	2114
Elongation %	136	1	14	24
100% Modulus; psi	1407	n/a	n/a	n/a
Hardness; Shore A	54	47	47	43
After 70 hours @ 175° C.
in Chrysler MS9602
Automatic Transmission Fluid
Tensile Strength; psi	1455	986	1153	1099
Elongation %	274	116	149	175
100% Modulus; psi	446	813	670	480
Hardness; Shore A	54	47	47	43
Volume Change; %	29	52	51	53

Levapren is a trademark of Bayer Corporation
Hypalon is a trademark of DuPont Dow Elastomers
Tyrin is a trademark of DuPont Dow Elastomers

Example 2



	Parts per hundred of polymer (phr)

Levapren ® 600 HV	100	75	50	25		75	50	25
Vamac ® PE 2166		25	50	75	100
Vamac ® DLS						25	50	75	100
Stearic Acid	1	1	1	1	1	1	1	1	1
Magnesium Oxide	10	10	10	10	10	10	10	10	10
N650 Carbon Black	70	70	70	70	70	70	70	70	70
Silicon Dioxide	5	5	5	5	5	5	5	5	5
Trioctyl Trimellitate	7.5	7.5	7.5	7.5	7.5	7.5	7.5	7.5	7.5
Adipate Plasticizer	2.5	2.5	2.5	2.5	2.5	2.5	2.5	2.5	2.5
1-Octadecanamine	1	1	1	1	1	1	1	1	1
Poly(oxy-1,2-ethanediyl),alpha-	1	1	1	1	1	1	1	1	1
octadecyl-omega-hydroxy,-phosphate
Triallyl Cyanurate, 72% Dispersion	1	1	1	1	1	1	1	1	1
N,N′-m-Phenylene Dimaleimide	1	1	1	1	1	1	1	1	1
Dicumyl Peroxide; 99%	2.4	2.4	2.4	2.4	2.4	2.4	2.4	2.4	2.4
4,4′-Di(methylbenzyl)diphenylamine	2	2	2	2	2	2	2	2	2
Cured 20 minutes @ 175° C.
Original Properties
Tensile Strength; psi	1806	1702	1486	1361	1054	1664	1482	1336	997
Elongation %	289	284	282	294	316	282	253	306	373
100% Modulus; psi	761	691	662	632	527	670	643	583	381
Hardness; Shore A	78	79	81	79	79	78	76	75	73
Compression Set, 70 h. @ 175° C.	49	62	67	73	76	66	71	80	90
After 168 hours @ 150° C. in Air
Tensile Strength; psi	1645	1432	1200	1045	929	1588	1501	1421	1149
Elongation %	285	311	332	300	336	293	240	271	336
100% Modulus; psi	925	863	782	689	689	924	905	954	735
Hardness; Shore A	83	84	85	90	90	86	84	86	83
After 70 hours @ 175° C. in Air
Tensile Strength; psi	1584	1477	1305	1186	1010	1587	1543	1493	1168
Elongation %	286	261	290	298	317	276	240	249	295
100% Modulus; psi	1041	1048	954	918	803	1008	1039	1123	830
Hardness; Shore A	87	90	91	91	92	88	88	88	90
After 336 hours @ 175° C. in Air
Tensile Strength; psi	1733	1844	1808	1531	1409	Not Tested	Not Tested	Not Tested	Not Tested
Elongation %	93	117	118	136	155
100% Modulus; psi	1453	1372	1324	1115	979
Hardness; Shore A	92	92	94	94	94
After 70 hours @ 162.8° C.
in Dexron ® III
Automatic Transmission Fluid
Tensile Strength; psi	1491	1419	1270	1220	989	1523	1502	1354	1124
Elongation %	280	252	283	273	318	280	276	271	324
100% Modulus; psi	508	519	457	476	403	439	517	557	482
Hardness; Shore A	54	54	58	58	63	63	59	66	74
Volume Change; %	34	28	26	24	20	25	19	13	6
After 70 hours @ 150° C. in IRM 903 Oil
Tensile Strength; psi	1281	1266	1159	1065	852	1310	1255	1120	1015
Elongation %	193	185	199	225	255	204	221	232	308
100% Modulus; psi	589	622	536	471	377	541	463	439	322
Hardness; Shore A	44	49	49	50	51	44	46	50	55
Volume Change; %	67	61	55	50	47	53	45	35	22

Levapren is a trademark of Bayer Corporation
Vamac is a trademark of E. I. Dupont de Nemours and Company, Inc.
Dexron is a trademark of General Motors Corporation

The percentages by weight of the various ingredients forming the automotive components of the present invention are defined as weight percent based upon the total weight of the elastomeric composition from which the automotive component is derived.
The ratios of ethylene and vinyl ester in the ethylene-vinyl ester copolymers are defined as mol percent.
While preferred embodiments of the invention have been described in detail and exemplified in the above examples and specification, it will be apparent to those skilled in the art that the invention may be modified without deviating from the scope of the invention. Therefore, the foregoing examples and description are to be considered exemplary rather than limiting and are not to be limited thereto.

Claims

1. A vulcanized, heat tolerant, pressure and hydrocarbon resistant elastomeric automotive component exhibiting improved hydrocarbon fluid impermeability, wherein said automotive component comprises:

about 10 to 50% by weight of a blend comprising a first ethylene-vinyl ester copolymer and a second polymeric member selected from the group consisting of an ethylene-acrylic elastomer, an alkyl acrylate copolymer, and mixtures thereof; and

about 25 to 75% by weight of a plurality of additives selected from the group consisting of process aids, fillers, plasticizers, metal oxides, metal hydroxides, peroxides, coagents, antioxidants and combinations thereof.

2. The automotive component of claim 1, wherein said first ethylene-vinyl ester copolymer is an ethylene-vinyl acetate copolymer and said second polymeric member is an ethylene-acrylic elastomer.

3. The automotive component of claim 2, wherein said ethylene-vinyl acetate copolymer contains about 40 to 90% vinyl acetate.

4. The automotive component of claim 2, wherein said ethylene-vinyl acetate copolymer contains about 50 to 80% vinyl acetate.

5. The automotive component of claim 2, wherein said blend contains about 10 to 90 weight percent ethylene-vinyl acetate copolymer and about 90 to 10 weight percent ethylene-acrylic elastomer.

6. The automotive component of claim 1 further comprising 0 to about 75% by weight of an elastomeric polymer selected from the group consisting of chlorinated polyolefin, chlorosulfonated polyolefin, polychloroprene, ethylene-acrylic rubber, alkyl acrylate copolymer, polyvinyl acetate, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, ethylene-propylene diene terpolymer, styrene-butadiene rubber, ethylene-propylene rubber, butyl rubber, cis-polybutadiene, cis-polyisoprene, polyurethane, polyamide and combinations thereof.

7. The automotive component of claim 1, wherein said one or more additives comprises:

about 0.1 to 8% by weight one or more processing aids selected from the group consisting of stearic acid, stearates, 1-octanedecanamine, polyethylene, amines, oils, organic esters, organic phosphate esters and combinations thereof;

about 20 to 60% by weight one or more fillers selected from the group consisting of carbon black, graphite, silicone dioxide, fumed silica, precipitated silica, diatomaceous earth, magnesium carbonate, calcium carbonate, magnesium silicate, aluminum silicate, titanium dioxide, talc, mica, aluminum sulfate, calcium sulfate, wollastonite, molybdenum disulfide, clay, calcium carbonate and combinations thereof;

about 3 to 15% by weight one or more plasticizers selected from the group consisting of hydrocarbons, glycols, aldehydes, ethers, esters, ether-ester, trioctyl trimellitate and combinations thereof;

about 0.1 to 10% by weight one or more metal oxides and/or hydroxides selected from the group consisting of zinc oxide, zinc hydroxide, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, aluminum hydroxide and combinations thereof;

about 0.5 to 4% by weight one or more peroxides selected from the group consisting of 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; a,a′-bis-(t-butylperoxy)-p-diisopropylbenzene; dicumyl peroxide; di-t-butyl peroxide; 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane; 2,4-dichlorobenzoyl peroxide; benzoyl peroxide; p-chlorobenzoyl peroxide; 4,4-bis(t-butylperoxy) valerate; t-butylcumyl peroxide; di-t-amyl peroxide; t-butyl hydroperoxide and combinations thereof;

about 0.1 to 5% by weight one or more coagents selected from the group consisting of maleimides, triallyl cyanurate, triallyl isocyanurate, diallyl terephthalate, 1,2-vinyl polybutadiene, di- and tri-functional methacrylates, diacrylates, metal ion versions thereof and combinations thereof; and

about 0.1 to 3% by weight one or more antioxidants selected from the group consisting of phenols, hydrocinnamates, hydroquinones, hydroquinolines, diphenylamines, mercaptobenzimidazoles and combinations thereof.

8. The automotive component of claim 7, wherein said composition comprises:

about 10 to 90% by weight of an ethylene-vinyl acetate copolymer, wherein said ethylene-vinyl acetate copolymer contains about 50 to 80% vinyl acetate;

about 90 to 10% by weight of an ethylene-acrylic elastomer;

about 0.2 to 0.7% by weight stearic acid;

about 23 to 38% by weight carbon black;

about 2 to 5% by weight silicon dioxide;

about 3 to 7% by weight trioctyl trimellitates;

about 0.1 to 7% by weight adipate type plasticizer;

about 0.1 to 8% by weight magnesium oxide;

about 0.1 to 0.75% by weight 1-octanedecanamine;

about 0.1 to 0.75% by weight organic phosphate ester;

about 0.5 to 4% by weight organic peroxide;

about 0.25 to 1% by weight triallyl cyanurate;

about 0.25 to 1% by weight N,N′, n-phenylenedimaleimide;

about 0.25 to 2% by weight antioxidant selected from the group consisting of phenols, hydrocinnamates, diphenylamines, hydroquinones, hydroquinones, hydroquinolines and mixtures thereof.

9. The automotive component of claim 1, wherein said automotive component is selected from the group consisting of automotive hoses, transmission belts, seals, dampers, engine mounts, air duct housing, gaskets and CV joint boots.

10. The automotive component of claim 9, wherein said automotive component is a hose.

11. A method for preparing a vulcanized, heat tolerant, pressure and hydrocarbon resistant automotive component having improved hydrocarbon fluid impermeability, said method comprising:

providing a first ethylene- vinyl ester copolymer; wherein said vinyl ester is a vinyl ester of a C₂to C₆lower carboxylic acid;

providing a second polymeric material comprising a polymeric material selected from the group consisting of ethylene-acrylic elastomer (AEM), alkyl-acrylate copolymer (ACM), ), and mixtures thereof;

providing one or more additives selected from the group consisting of process aids, fillers, plasticizers, metal oxides, metal hydroxide, peroxides, coagents, antioxidants and combinations thereof;

blending said first ethylene-vinyl ester copolymer, said second polymeric material, and said one or more additives to form an elastomeric composition comprising said first ethylene-vinyl ester copolymer, said second polymeric material, and said; one or more additives;

forming said automotive component from said elastomeric composition; and

vulcanizing said automotive component.

12. The method of claim 11, wherein said ethylene-vinyl ester is ethylene-vinyl acetate and said second polymeric material is an ethylene-acrylic elastomer.

13. The method of claim 12, wherein said ethylene-vinyl acetate contains about 40 to 80% vinyl acetate.

14. The method of claim 12, wherein said ethylene-vinyl acetate copolymer contains about 50 to 80% vinyl acetate.

15. The method of claim 12, wherein said elastomeric composition comprises about 10 to 90% by weight said first ethylene-vinyl ester copolymer; about 90 to 10% second polymeric material, and about 25 to 75% by weight of one or more additives.

16. The method of claim 11, further comprising about 0 to about 75% by weight of an elastomeric polymer selected from the group consisting of chlorinated polyolefin, chlorosulfonated polyolefin, polychloroprene, polyvinyl acetate, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber and combinations thereof.

17. The method of claim 11 wherein one or more of said additives comprises:

about 0 to 8% by weight one or more processing aids selected from the group consisting of stearic acid, stearates, 1-octanedecanamine, polyethylene, amines, oils, organic esters, organic phosphate esters and combinations thereof;

about 0 to 10% by weight one or more metal oxides and/or hydroxides selected from the group consisting of zinc oxide, zinc hydroxide, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, aluminum hydroxide and combinations thereof;

about 0 to 5% by weight one or more coagents selected from the group consisting of maleimides, triallyl cyanurate, triallyl isocyanurate, diallyl terephthalate, 1,2-vinyl polybutadiene, di- and tri-functional methacrylates, diacrylates, metal ion versions thereof and combinations thereof; and

about 0 to 3% by weight one or more antioxidants selected from the group consisting of phenols, hydrocinnamates, hydroquinones, hydroquinolines, diphenylamines, mercaptobenzimidazoles and combinations thereof.

18. The method of claim 17, wherein said composition comprises:

about 10 to 90% by weight of an ethylene-vinyl acetate copolymer containing about 50 to 80% vinyl acetate;

about 90 to 10% by weight of an ethylene-acrylic elastomer;

about 0.2 to 0.7% by weight stearic acid;

about 23 to 38% by weight carbon black;

about 2 to 5% by weight silicon dioxide;

about 3 to 7% by weight trioctyl trimellitate;

about 1 to 7% by weight adipate type plasticizer;

about 1 to 8% by weight magnesium oxide;

about 0.1 to 0.75% 1-octanedecanamine;

about 0.1 to 0.75% organic phosphate ester;

about 0.5 to 4% by weight organic peroxide;

about 0.25 to 1% by weight triallyl cyanurate;

about 0.25 to 1% by weight N,N′, n-phenylenedimaleimide;

about 0.25 to 2% by weight antioxidant selected from the group consisting of phenols, hydrocinnamates, diphenylamines, hydroquinones, hydroquinolines and mixtures thereof.

19. The method of claim 11, wherein said automotive component is selected from the group consisting of hoses, belts, seals, dampers, engine mounts, and CV joint boots.

20. The method of claim 19, wherein said automotive component is hoses, said method further comprising applying a reinforcing layer comprising natural or synthetic fibers selected from the group consisting of cotton, polyester, nylon, rayon, and aramid; or metal wire, said method further comprising applying a cover layer on an outer surface of said reinforcing layer, said cover layer comprising a synthetic elastomer selected from the group consisting of styrene-butadiene rubber, butadiene-acrylonitrile rubber, chloroprene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, epichlorohydrin-ethylene oxide copolymer, polyvinyl chloride, and blends thereof.

21. In a vulcanized hose for conveying fluids in an automotive engine cooler, transmission oil cooler, power transmission cooler, radiator or heater, the improvement which comprises employing as an inner tubular structure of the hose, a heat tolerant, pressure and hydrocarbon resistant composition exhibiting improved hydrocarbon fluid impermeability compared to conventional hose-forming compositions, wherein said composition comprises:

about 10 to 90% by weight of a n ethylene-vinyl acetate copolymer containing about 50 to 80% vinyl acetate;

about 90 to 10% by weight of an ethylene-acrylic elastomer;

about 0.2 to 0.7% by weight stearic acid;

about 23 to 38% by weight carbon black;

about 2 to 5% by weight silicon dioxide;

about 3 to 7% by weight trioctyl trimellitate;

about 1 to 7% by weight adipate type plasticizer;

about 1 to 8% by weight magnesium oxide;

about 0.1 to 0.75% by weight 1-octanedecanamine;

about 0.1 to 0.75% by weight organic phosphate ester;

about 0.5 to 4% by weight organic peroxide;

about 0.25 to 1% by weight triallyl cyanurate;

about 0.25 to 1% by weight N,N′, n-phenylenedimaleimide;

about 0.25 to 2% by weight antioxidant selected from the group consisting of phenols, hydrocinnamates, diphenylamines, hydroquinones, hydroquinolines and mixtures thereof. said hose further including a reinforcing layer over said tubular structure, said reinforcing layer comprising natural or synthetic fibers selected from the group consisting of cotton, polyester, nylon, rayon and aramid; or metal wire, and a cover layer over said reinforcing layer, said cover layer comprising a synthetic elastomeric selected from the group consisting of styrene-butadiene rubber, butadiene-acrylonitrile rubber, chloroprene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, epichlorohydrin-ethylene oxide copolymer, polyvinyl chloride, and blends thereof.