MXPA06005948A - Fluid and heat resistant chlorinated polyethylenes. - Google Patents

Abstract

A chlorinated rubber composition which is resistant to various fluids such a s transmission fluids comprises a blend of a chlorinated polyethylene elastome r, an ethylene acrylic elastomer and/or polyacrylic rubbers, and optionally a chlorosulfonated polyethylene. The rubber composition has many uses such as a tube and generally contains various additives such as fillers, plasticizers, vulcanizing agents, and the like. A heat resistant rubber composition comprises a blend of a chlorinated polyethylene elastomer, an ethylene-acrylic elastomer and/or polyacrylic rubbers, an ethylene-octene copolymer, and an ethylene-propylene-diene terpolymer, and t he same can be used as a cover or jacket as on the above chlorinated rubber tube.

Description

CHLORINATED POLYETHYLENE RESISTANT TO LIQUIDS AND HEAT Field of the Invention The present invention relates to chlorinated polyethylene rubber compositions, which have a good resistance to liquids, for example, automatic transmission liquids and have good resistance to high heat. BACKGROUND OF THE INVENTION To date, numerous rubber compounds have been used as sheets, pipes, coatings and the like. However, there have generally been no chlorinated polyethylene rubber compositions which had good resistance to transmission fluids, especially for the recent types of "E-liquids". Similarly, although numerous types of rubbers resistant to high temperatures were available, mixtures of a chlorinated polyethylene elastomer, an ethylene-octene copolymer and an ethylene-acrylic and / or polyacrylic elastomer were generally not known. which have a good heat resistance of about 150 ° C. SUMMARY OF THE INVENTION Fluid-resistant rubbers generally comprise 70 parts by weight of chlorinated polyethylene and from about 5 to about 49 parts by weight of an ethylene-acrylic elastomer having a Mooney viscosity (ML 1 + 4/100 ° C) of from about 10 to about 25 and / or a polyacrylic elastomer having a Mooney viscosity of from about 10 to about 70. Rubber compositions having a good high heat resistance generally comprise 70 parts by weight of a chlorinated polyethylene rubber containing from about 25% to about 45% chlorine by weight, from about 5 to about 49 parts by weight of an ethylene-octene copolymer having an octene content of from about 25% to about 55% by weight and from about 5 to about 49 parts by weight of an ethylene-acrylic elastomer having a Mooney viscosity of from about 10 to about 25 and / or a polyacrylic rubber. It has a Mooney viscosity of from about 10 to about 70 and optionally from about 10 to about 50 parts by weight of the EPDM rubber containing from about 30% to about 70% by weight of ethylene repeating units and from about 0.1% up to about 8% of diene repeat units.

Detailed Description of the Invention Com positions of Liquid Resistant Hu The different components of the chlorinated composition are based on 70 parts by weight of at least one chlorinated polyethylene elastomer. The chlorinated elastomer generally contains from about 25% to about 50% by weight, desirably from about 30% to about 45% by weight and preferably from about 36% to about 42% by weight of chlorine in it. Examples of suitable chlorinated polyethylene elastomers are known to the literature and to the art and specific commercial examples of such compounds include Tyrin CM 0836, which contains about 36% by weight of chlorine and has a viscosity of Mooney. (ML 1 + 4/1 00 ° C) of about 1 00, Tyri n CM 01 36, which contains approximately 36% by weight of chlorine and has a Mooney viscosity of about 80, and Tyrin CM 421 1 P, which contains approximately 42% by weight of chlorine and has a Mooney viscosity of about 80. All chlorinated polyethylene elastomers Tyrin can be obtained at Du Pont Dow. When referring to a Mooney viscosity in the present invention, it is found in a viscosity of Mooney of (ML 1 + 4 / 100JC). An important aspect of the chlorinated polyethylene elastomers of the present invention is that they can be desirably cured by peroxides, such as those set forth below, as well as by different thio compounds, such as thiazole derivatives and also by irradiation. If two or more chlorinated polyethylene elastomers are used, the range of any elastomer may generally be from about 1% to about 99% by weight and desirably from about 25% to about 75% by weight based in the total weight of all chlorinated polyethylene elastomers. Another important component of the chlorinated composition is at least one ethylene-acrylic elastomer wherein the acrylic can be an alkyl acrylate wherein the alkyl portion desirably has from about 1 to about 8 carbon atoms and preferably It's methyl acrylate. The ethylene-acrylic elastomer generally has a Mooney viscosity of about 10 to about 25 and desirably about 1 3 to about 1 9. The total amount of one or more ethylene-acrylic elastomers is generally found in a quantity of approximately 5 to approximately 49 parts, so of about 5 to about 40 parts and preferably about 25 to about 35 parts by weight per 70 parts by weight of said or more chlorinated polyethylene elastomers. Examples of suitable ethylene-acrylic elastomers include the different Vamac elastomers which are available from Du Pont Polymers, such as Vamac D, Vamac DLS, Vamac G, Vamac GLS and Vamac HG, Vamac D being highly preferred. P. Instead of the ethylene-acrylic elastomer in any portion therewith, one or more polyacrylate elastomers may be used, which are known in the art and for the literature. Generally, polyacrylate elastomers contain alkyl acrylate repeat units wherein the alkyl portion is desirably 1 to about 8 carbon atoms and preferably is methyl acrylate or ethyl acrylate. Generally also minor amounts of alkoxy acrylates are used wherein the alkoxy portion generally has from 1 to 5 carbon atoms with the preferred being methoxy and ethoxy. The Mooney viscosity of the one or more acrylate elastomers is generally from about 10 to about 70 and preferably from about 25 to about 40 or 55. The amount of the polyacrylic elastomers is generally from about 5 to about 49 parts, desirably give about 5 to about 40 parts and preferably about 25 to about 35 parts by weight per 70 parts by weight of the chlorinated polyethylene elastomers. The polyacrylic elastomer can be used, either in place of one or more ethylene-acrylic elastomers or partially substituted by them. In other words, any combination of ethylene-acrylic elastomers or polyacrylic elastomers can be used with the total amount of both being from about 5 to about 49 parts by weight, desirably from about 5 to about 40 parts by weight and preferably from about 25 to about 35 parts by weight per 70 parts by weight of the polychlorinated polyethylene elastomers. Whenever the present invention relates generally to the peroxide cure, polyacrylates are used which can be cured by means of a peroxide. Because the polyacrylates have a saturated structure, cross-linking is achieved by the incorporation of a co-polymerized reactive curation site, such as through the use of suitable peroxide reactive compounds, such as carboxylic acid and the like. A suitable polyacrylic elastomer is HyTemp PV-04 manufactured by Zeon Chemicals. An optional, but desirable component of The chlorinated rubber composition is a chlorosulfonated polyethylene which generally contains from about 25% to about 45%, desirably from about 30% to about 40% and preferably from about 33% to about 38% by weight of chlorine in it. The amount of sulfur is generally very low from about 0.25% to about 2%, desirably from about 0.5% to about 1.5%, and preferably from about 0.75% to about 1.25% by weight based on the total weight of chlorosulfonated polyethylene. One or more chlorosulfonated polyethylenes when generally used are from about 5 to about 49 parts by weight, desirably from about 10 to about 40 and preferably from about 25 to about 35 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene elastomers. Examples of such suitable compounds include the various Hypalon compounds that are available from DuPont Dow, such as Hypalon 20, Hypalon 30, with Hypalon 40 being preferred which contains about 35% chlorine by weight and about 1% by weight. Sulfur weight. The chlorinated rubber composition of the present invention is composed generally using conventional additives known in the art for the literature, such as activators and / or acid expellers, processing aids, different fillers, which may also serve as reinforcement aids, plasticizers, vulcanization compounds, such as different peroxides, co-agents such as cure activators, lubricants, stabilizers and the like. Acid activators and / or expellers include various metal hydroxyl and / or carbonates, such as magnesium hydroxy aluminum carbonate, metal oxides, such as magnesium dioxide, lead oxide, organic lead bases and the like. A preferred acid activator / expeller is Maglite D or DE produced by C.P. Hall Company. The total amount of said activator and / or acid scavenger is generally low, so that it will be from about 3 to about 20 and from about 5 to about 15 parts by weight per 70 parts by weight of said one or more polyethylene elastomers. chlorinated Process aids include various waxes, such as low molecular weight polyethylene waxes, polystyrene waxes, paraffin waxes, fatty acids and the like, with polyethylene waxes being preferred. The adequate quantities of the processing aid are generally they range in a range from about 0.1 to about 10 and desirably from about 1 to about 5 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene elastomers. Suitable fillers include Caolin clay, mica, calcium, carbonate and the like. The amount of such fillers is generally from about 5 to about 80 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene elastomers. Reinforcing fillers, such as carbon black preferably have a high surface area and iodine numbers of from about 25 to about 32. Specific examples include an N762, N774, N550 and N990 produced by Cancarb. The amount of the reinforcing agent is generally high from about 50 to about 300 parts by weight, desirably from about 1 00 to about 250 parts by weight and preferably from about 125 to about 200 parts by weight per 70 parts by weight. of one or more chlorinated polyethylene elastomers. Numerous types of plasticizers can be used to impart stability to light and heat, such as one or more epoxidized soy bean oils, various phthalates, such as diallyl phthalate, d-2-ethylhexyl phthalate, diisopropyl phthalate, linear Cs-C-io phthalates and linear C7-Cn phthalates; various trimellitATES, such as tr? -2-ethyl hexyl trimellitate, triisooctyl trimellitate and triisononyl trimellitates; various adipates such as diisooctyl adipate, di-2-ethylhexyl adipate, diisononyl adipate and diisodecyl adipate; various azelates, such as di-2-ethylhexyl azelate; various glutarates, such as diisodecyl glutarate and various sebacates, such as di-2-ethylhexyl sebacate. The total amount of the one or more different types of plasticizers is generally from about 1 to about 60 parts by weight and desirably from about 7 to about 50 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene elastomers. The vulcanization compound is desirably a peroxide and numerous types thereof and in the literature are known in the art. Examples of suitable peroxides include 4,4-bis (tert-butyl peroxy) butyl valerate, t-butyl perbenzoate, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexin, n-butyl -4, 4-bis (t-butylperoxy) vale while, 1, 1-bis (t-butylperoxy) 3,3,5-trimethyl ciciohexane, di- (2-tert-butylperoxyisopropyl) benzene dibenzoyl peroxide, 2,5- dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide and combinations thereof. Preferred peroxides include 2,2'-bis (tert-butylperoxydiisopropylbenzene) and 1-1-di (tert-butylperoxy) -3,3,5-trimethylcyclylhexane respectively available as Vulcup 40KE and Trigonox 20-40B-PD, both of which can be obtained from Harwick Standard. A total amount of the one or more vulcanization compounds is generally from about 0.1 to about 10 and desirably from about 3 to about 6 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene elastomers. Co-agents generally include two types serving Type I to improve the cure condition and also the rate of reaction while Type II generally only affects the cure condition. Examples of suitable Type I co-agents include methacrylate products, such as trimethylolpropane trimethacrylate (TMPTMA) and various Bis-maleimides, such as N, N'-m-phenylene dimaleimide (HVA-2) and various acrylates, such as trimethylolpropane triacrylate (TMPTA). Suitable Type II co-agents include triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), diallyl terephthalate and 1,2-ViniI polybutadienes (Ricons) and the like. There are numerous other co-agents and they are known in the art and literature. The total amount of the one or more co-agents is generally from about 0.1 to about 15 parts by weight and desirably from about 3 to about 12 parts by weight per 70 parts by weight of said one or more polyethylene elastomers. chlorinated. The various compounds and foregoing components are compounds and subsequently formed into the desired end-use forms, such as a tube. More specifically, a process of making the desired compound comprises mixing all non-curable compounds (other than vulcanizing agents and co-agents) in any order in a continuous high-cut mixer being added at the end one or more polymers. Therefore, in any order, the one or more acid activators and / or expellers and the one or more processing aids, the one or more fillers, such as a reinforcing filler and the one or more plasticizers are added alone in any order with continuous mixing until all of them have been added and mixed in a high cut mixer. Generally, any high shear mixer is suitable and in the following examples a Thyssen Krupp GK 250 F was used. After all the different additives have been added and mixed, the polymers, ie the one or more chlorinated polyethylene elastomers. , the one or more optional chlorosulfin polyethylenes and the one or more ethylene-acrylic elastomers are generally added in any order and mixed until a generally homogeneous mixture is obtained. The composite rubber can then be cooled in any way and deposited on a plate which, desirably, has an anti-breakage agent on the surface thereof. When desired, the composite chlorinated rubber composition of the present invention is then added to a high shear mixing apparatus, which may be the same as or different to that used in forming the rubber compound and is mixed with the one or more agents of vulcanization and the one or more co-agents at a low temperature, so that the composition is not cured. The composite rubber containing the cure additives can be formed into any desired shape, such as a tube using an extruder. The chlorinated rubber compositions of the present invention generally have a good shelf life of about 35 to about 45 days, where they can be transferred to a final manufacturer and cured at suitable temperatures. Suitable final shapes include sheets, tubes, hoses and gaskets. A desired end use of the chlorinated rubber compositions of the present invention is as a hose or as a tube to be used for transporting vehicle transmission fluids and especially E-type transmission fluids, provided that the composite rubbers have good strength. to them. One specification of the automatic transmission "E" liquid is WSA-M96D26-A from Ford Motor Company. Bliss The specification is substantially reproduced in the present document as follows: HOSE, REINFORCED RUBBER, RESISTANT TO AUTOMATIC TRANSMISSION LIQUID WSA-M96D26-A 1. SCOPE This description defines a synthetic rubber hose formed or straight reinforced with a single layer of rubber. textile braided and with resistance to automatic transmission fluid. 2. APPLICATION The present description was originally released for a hose of an automatic transmission oil cooler. The hose is resistant to long-term exposure to automatic transmission fluid up to 150 ° C and an air temperature of up to 125 ° C. For applications that require air temperatures above 125 ° C, consider model WSD-M96D13-A. 3. REQUIREMENTS 3.1 QUALITY SYSTEM REQUIREMENTS Materials suppliers and parts producers must comply with the QS-9000 Quality System Requirements. The material specification requirements are going to be used for the initial qualification of the materials. A Control Plan is required for the verification of the production in progress. This plan must be reviewed and approved by the important Ford Materials activity and / or the Ford Supplier Technical Assistance (STA) before the production parts presentation. The appropriate statistical tools should be used to analyze the process / product data and ensure consistent processing of the materials. Producers of parts that use this material in their products must use materials approved by Ford and must comply with a process control plan, which has been approved by the STA and / or the Material Materials Activity. 3.2 INFRARED SPECTROPHOTOMETRY AND / OR THERMAL ANALYSIS Ford Motor Company, at its option, may perform infrared and / or thermal analysis of the materials / parts supplied for this specification. The IR spectra and the thermograms established for the initial approval must constitute the reference standard and must be kept in the file in the designated materials laboratory. All samples should produce IR spectra and thermograms that correspond to the reference standard when tested under the same conditions. 3.3 CONDITIONING AND TEST CONDITIONS All the test values indicated here are based on materials conditioned in a controlled atmosphere of 23 +/- 2 C and 50 +/- 5% relative humidity for less than 24 hours before the test and tested under the same conditions unless otherwise specified contrary. 3.4 CONSTRUCTION OF THE HANDLE The hose should consist of a smooth central synthetic rubber tube and be covered with synthetic oil-resistant rubber at high temperature (see paragraph 5.2). The tube must be covered with a single layer of a suitable braided reinforced textile. The hose must be coupled with final accessories of bent metal. 3.5 EBA D E MATERIALS The following tests must be carried out on the finished hoses and / or the test samples cut from them. The test samples must be cut by die of the finished parts and divided or cut to the required thickness, where necessary,. When this is not possible, samples cut from molded test plates manufactured from the same material should be used with an equal cure condition. The test plates should have the following dimensions: 1 50 x 1 50 mm, minimum by 2.0 +/- 0.2 mm. 3.6 ORIGINAL PROPERTIES 3.7 AGED PROPERTIES , 8 FINISHED PART This requirement is only applicable when couplings are used with the hose. The assemblies must withstand a minimum pull of 1.1 kN without separating the couplings from the hose, without filtering the coupling connection or breaking the hose.

Test Method: The hose assembly must be filled with the approved automatic transmission fluid of the current production (see paragraph 5.1), closed at both ends and aged by heat at a temperature of 150 +/- 2 ° C for 24 hours . The aged assemblies, after cooling to a temperature of 23 +/- 2 ° C, should be conditioned at a temperature of -40 +/- 1 ° C for 24 hours. After conditioning and while still in the cooling box, the hose assembly must be folded around a mandrel conditioned for temperature, which has a radius equal to the minimum bending radius of 10 times the bending of the inner diameter. which should be done within 4 s. 3,8.5 Accelerated Impulse Test Test Method: Hose assemblies and / or uncoupled hose d, where applicable, should be previously conditioned by filling it with the tested automatic transmission fluid of the current production (see paragraph 5.1), closed at both ends and aged by heat at a temperature of 150 +/- 2 ° C for 70 hours before the impulse test. For the initial qualification, the aged hose assemblies must withstand 250,000 impulse cycles at a maximum working pressure of 1.1 MPa without bursting or showing any signs of failure. Hose assemblies removed from the test apparatus and tested for burst pressure shall not average more than 20% below the average of the original results in accordance with paragraph 3.8.1. Subsequent periodic certification tests should require aged assemblies to withstand 100,000 impulse cycles at a maximum working pressure of 1.1 MPa without failure, while maintaining transmission fluid temperatures at 150 ° C and in the ambient air chamber at 125 ° C. The values of resistance to bursting of the hose assemblies after finishing the 100,000 impulse cycles, should not average more than 15% below the average of the original results (see paragraphs 3.8.1 and 3.8.3). 3,8,5,1 Resistance to Oil and Heat After successfully completing the 100,000 impulse cycles according to paragraph 3.8.5, the ASTM standardized samples taken from the hose should not exceed the following values: 3,8,6 Resistance to Entangle Test Method: The length of the required hose of the test insert insert secures each end with metal clamps. When the hose is installed, it must be bent within 5 seconds in the same plane and direction as its free condition curvature. Place the attachment in an oven at a temperature of 120 +/- 2 ° C for 1 hour. The attachment is removed from the oven and within 5 minutes a steel ball of the specified diameter is passed through the hose installed in the attachment. The ball must pass freely.

Sample Selection: The production hose selected from the test so as not to become entangled, should represent, as close as possible, a minimum thickness of the wall. When the results are recorded, they include the thickness of the wall, the ovality and an "A" dimension (see previous paragraphs). This dimension is measured while the sample is not found in the test attachment.

The present invention will be better understood by reference to the following examples, which serve to illustrate the invention, but not to limit it. TABLE 1 EXAMPLES The different ingredients of Table 1 were compounded in a manner as stated above. That is, all non-curable components were added one by one to a high-cut mixer such as one made by Farrel or Krupp and blended with the polymers added at the end. The total mixing time was generally about 3 up about 10 minutes with a time of about 4 minutes being preferred and the mixing temperature of the mixer was 121.11 ° C (250 ° F) to about 160 ° C (320 ° F) with about 300.89 ° C (300 ° F) being preferred. . After cooling and plate formation, the chlorinated polyethylene composition was then mixed with the indicated curing agents at a low temperature of about 93.33 ° C (200 ° F) to 121.11 ° C (250 ° F) and then extruded into the shape of a tube. Subsequently, the tube was cured at a temperature of approximately 173.89 ° C (345 ° F) for approximately 13 minutes and tested. Examples 1, 3 and 4 were rubber compositions tested after several runs of production while Example 2 was a rubber composition made in the form of a hose and taken out of production and tested. The following properties were obtained.

TABLE 2 Examples 1 to 4 gave excellent results with respect to little change in various properties, such as tensile strength, elongation, hardness and percentage volume at high temperatures. In addition, said pipe passed the tests of transmission fluids of type "E".

High Heat Resistant Compositions The formulations of the high heat resistant rubber compositions are based on 70 parts by weight of one or more chlorinated polyethylene elastomers. The amount of chlorine in the elastomer is generally from about 20% to about 45% by weight and preferably from about 25% to about 30% by weight. If two or more different chlorinated polyethylene elastomers are used, the amount of one of the elastomers is generally from about 1% to about 99%, and desirably, from about 25% to about 75% by weight. weight based on the total weight of the chlorinated polyethylene elastomers. Said elastomers are known in the art and for the literature. Examples of suitable chlorinated polyethylene elastomers include Tyrin CM 0730 which contains about 30% by weight of chlorine and has a Mooney viscosity (ML 1 + 4/1 00 ° C) of about 65, Tyrin CM 0836 which contains about 36% by weight of chlorine and has a Mooney viscosity of about 1 00, and Tyrin CM 01 36 which contains about 36% by weight of chlorine and has a Mooney viscosity of about 80. Tyri n chlorinated polyethylene elastomers are produced by Du Pont Dow.

An important aspect of the present invention is to use an ethylene-octene copolymer in an amount of about 5 to about 49 parts by weight, desirably about 12 to about 30 and preferably about 10 to about 20 parts by weight per 70. parts by weight of one or more chlorinated polyethylene elastomers. Such copolymers generally contain from about 25% to about 55% by weight and desirably from about 35% to about 45% by weight of octene units. Desirably the copolymers have a low specific gravity of about 08.5 to about 08.7 and have a melt index of about 0.25 to about 5.0 dg / min. Said copolymers are obtained as bonded polymers produced by DuPont Dow, such as the CL 8001 Engaged, CL 8002 Engaged, EG 8200 Engaged and preferably the EG 8150 Engaged. An important component used to form a high heat resistant rubber composition generally comprises one or more ethylene-acrylic elastomers wherein the acrylic portion may be an alkyl acrylate wherein the alkyl desirably has from about 1 to about 8 carbon atoms. carbon and preferably it is methyl acrylate. Ethylene-acrylic elastomers generally have a Mooney viscosity of about 10 to about 25 and preferably about 1 3 to about 1 9. The total amount of the one or more ethylene-acrylic elastomers is generally about 5. to about 49 parts, desirably, from about 5 to about 35 parts and preferably from about 10 to about 30 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene elastomers. Examples of suitable elastomers include Vamac D, Vamac DLS, Vamac G, Vamac GLS, and Vamac HG with Vamac DP being highly preferred. In place of the ethylene-acrylic elastomer or in any portion therewith, one or more polyacrylate elastomers may be used, which are known in the art and for the literature. Generally, polyacrylate elastomers contain a repeating alkyl acrylate ions wherein the alkyl portion desirably has 1 to 8 carbon atoms and is preferably methyl acrylate or ethyl acrylate. Generally, minor amounts of alkoxy acrylates may also be used, wherein the alkoxy portion generally has from 1 to 5 carbon atoms with methoxy or ethoxy being preferred. Mooney viscosity of the one or more acrylate elastomers is generally from about 10 to about 70 and preferably from about 25 to about 40 or 55. The amount of the polyacrylic elastomers is generally from about 5 to about 49 parts, desirably from about 5 to about 35 parts and preferably from about 10 to about 30 parts by weight per 70 parts by weight of said chlorinated polyethylene elastomers. The polyacrylic elastomer can be used, either in place of one or more ethylene-acrylic elastomers or to partially replace them. In other words, any combination of ethylene-acrylic elastomers or polyacrylic elastomers can be used, the total amount of both being from about 5 to about 49 parts by weight, desirably from about 5 to about 35 parts by weight and preferably from about 10 to about 30 parts by weight per 70 parts by weight of said polychlorinated polyethylene elastomers. Because the present invention generally refers to peroxide, polyacrylates are used, which can be cured by peroxide. Because the polyacrylates have a saturated structure, the crosslinking is achieved by the incorporation of a co-polymerized reactive cure site, such as through the use of suitable peroxide reactive compounds, such as carboxylic acid and the like. A suitable polyacrylic elastomer is a HyTem p PV-04 manufactured by Zeon Chemicals. An optimum component of the high heat resistance composite is the different EPDM polymers wherein the amount of ethylene repeat groups is generally from about 30% to about 70% and preferably about 35% at about 60% by weight, and wherein the amount of the diene is generally from about 0.1% to about 8% and desirably from about 0.2% to about 2% by weight based on the total weight of the copolymer. The amount of the EPDM rubber is generally from about 10 to about 50 parts by weight, desirably from about 12 to about 35 parts by weight and preferably from about 1 to about 25 parts by weight per 70 parts by weight of the one or more. more chlorinated polyethylene elastomers. A preferred commercial example of said compound is Nordel I P N DR-125 produced by R. T. Vanderbilt. An optional component of the chlorinated compound is a chlorinated polyethylene which generally contains about 25% a about 45%, desirably from about 30% to about 40% and preferably from about 33% to about 38% by weight of chlorine therein. The amount of sulfur is generally very low as from about 0.25% to about 2%, desirably from about 0.5% to about 1.5%, and preferably from about 0.75% to about 1.25% by weight based on the total weight of the chlorinated polyethylene. When used or more chlorosulfonated polyethylenes are generally present in an amount of about 5 to about 49 parts by weight, desirably 10 to about 40, and preferably about 25 to about 35 parts by weight per 70. parts by weight of said one or more chlorinated polyethylene elastomers. Examples of such suitable compounds include the various Hypalon compounds manufactured by D u Pont Dow, such as Hypalon 20, Hypalon 30, with Hypalon 40 being preferred, which contains about 35 wt% chlorine and about 1 wt% of sulfur. One or more anti-oxidants are used to help spread the resistance to high heat. There are numerous antioxidants and the same are known in the art and for the literature. The specific examples Preferred such compounds include Tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane mixed with pentaerythritol tris ester and 3- (3,5-di- (ter) -butyl- 4-hydroxyphenyl) proionic; Tiodiethylene Bis (3,5-Di (ter) -ButiI-4-hydroxyhydrocinnamate, and the like.) The total amount of said one or more compounds is generally from about 0.1 to about 4 and preferably from about 0.5 to about 2 parts by weight per 70 parts by weight of the one or more chlorinated polyethylene elastomers Commercial examples of said antioxidants include Irganox 1010 and Irganox 1035 produced by Ciba Specialty Chemicals.High heat resistant rubber compositions may generally contain conventional additives known in the art and for These additives can be the same as those previously established, that is, different activators and / or acid expellers, processing aids, different fillers which also serve as reinforcement aids, plasticizers, vulcanization compounds and co-agents such as activators, lubricants, stabilizers and the like. Such additives were later established with respect to the liquid-resistant chlorinated rubber compositions, they are generally completely incorporated as a reference.

Generally the same types of additives can be used and the amounts of the different additives are generally the same. However, with respect to carbon black, a smaller amount is generally used as from about 40 to about 200 parts by weight and desirably from about 70 to about 150 parts by weight per 70 parts by weight of the one or more elastomers of chlorinated polyethylene. In addition, the amount of calcium carbonate fillers is generally from about 5 to about 50 parts by weight and desirably from about 10 to about 40 parts by weight per 70 parts by weight of the one or more chlorinated polyethylene elastomers. Different vulcanization agents can be used, as well as co-agents (accelerators). There are numerous such compounds and they are known for the art and literature. With respect to the specific chemical examples and specific commercial examples, generally the same compounds as set forth above can be used with respect to the chlorinated rubber compositions and generally the same amounts of vulcanizing agents and co-agents can be used. Accordingly, they are incorporated in the present description completely as a reference.

A preferred end use of the present invention is to co-extrude the high heat resistant rubber composition around a liquid-resistant chlorinated polyethylene rubber composition in the form of a tube to form a rolled tube, hose or the like . In order to impart resistance to the hose, reinforcing fibers, either non-woven or preferably woven, can be used. A preferred end use is a formation of a hose for use with a liquid or automatic transmission of a vehicle, such as the E-type liquid already mentioned above. The present invention will be better understood by reference to the following example, which serves to illustrate but not to limit the present invention. In the composition of the high heat resistant rubber formation of Table 3, the different additives are added in any order, one by one to a high cut mixer followed by the addition of the different polymers, such as, for example, a the time and they are mixed at a suitable temperature and time to achieve a mixture of a high heat resistant rubber composition. The process of making the compound is essentially the same as stated above with respect to the chlorinated polyethylene rubber composition resistant to liquids. Therefore, the same high cut mixer can be used. The The mixing temperature of the high cut mixer with respect to the high heat resistant rubber composition is generally from about 121.11 ° C (250 ° F) to about 110 ° C (230 ° F), with about 148.89 ° C being preferred. (300 ° F) and the type of mixture can vary from about 3 to about 10 minutes with about 4 minutes being preferred. As with the previous one, once the composition is mixed, it can be cooled and stored. At some later time, the one or more vulcanization agents and coagents are added and mixed at a low temperature, such as from about 93.33 ° C (200 ° F) to about 121.11 ° C (250 ° F) so as not to cure the rubber. Once it is desired to form the final product, the high heat resistant rubber compositions containing the curing compounds therein can be mixed at a higher temperature and formed or given the proper final product form and cured as in a temperature of about 165.56 ° C (330 ° F) to about 182.22 ° C (360 ° F), for about a period of time from 10 to about 18 minutes. Suitable end products include sheets, linings for existing pipes or hoses, gaskets and the like.

TABLE 3 When the rubber composition resistant to high heat was prepared and tested, the following data were obtained: TABLE 4 As can be seen in the above data, the chlorinated polyethylene rubber composition for high heat has small changes in different properties, such as tensile strength, stretch and hardness, when tested for 168 hours at a temperature of 150 ° C. Although according to the patent statutes the best embodiment and preferred embodiment have been set forth above, it is not intended that the scope of the present invention be limited thereto, but only by the scope of the appended claims.

Claims (28)

1. CLAIMS 1. A curable rubber composition which comprises: at least one chlorinated polyethylene elastomer having from about 25% to about 50% chlorine by weight, the amount of said one or more chlorinated polyethylene elastomers is 70 parts by weight; at least one ethylene-acrylic elastomer having a Mooney viscosity of about 10 to about 25 and / or at least one polyacrylic elastomer having a Mooney viscosity of about 10 to about 70, the total amount of said one being or more ethylene-acrylic elastomers and / or said at least one polyacrylic elastomer of from about 5 to about 49 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene elastomers, and optionally at least one chlorosulfonated polyethylene which has from about 25% to about 45% chlorine by weight and from about 0.25% to about 2.0% sulfur by weight, the total amount of said at least one chlorosulfonated polyethylene being from about 5 to about 49 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene elastomers.
2. 2. A curable rubber composition as described in claim 1, characterized in that the chlorine amount of said chlorinated polyethylene composition is from about 30% to about 45% by weight.
3. 3. A curable rubber composition as described in claim 2, characterized in that the ethylene-acrylic elastomer has a Mooney viscosity of about 13 to about 19 and wherein the polyacrylic elastomer has a Mooney viscosity. from about 25 to about 55 and wherein the amount of said ethylene-acrylic elastomer and / or said polyaeryl elastomer is from about 5 to about 40 parts by weight.
4. 4. A curable rubber composition as set forth in claim 3, which includes carbon black in an amount of about 50 parts to about 300 parts by weight per 70 parts by weight of said one or more elastomers chlorinated polyethylene; and including a plasticizer in an amount of about 1 to about 60 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene elastomers.
5. 5. A rubber composition that can be cured such and as described in claim 4, characterized in that the chlorine amount of said chlorinated polyethylene elastomer is from about 36% to about 42% by weight, wherein the amount of said ethylene-acrylic elastomer and / or polyacrylic elastomer is from about 25 to about 35 parts by weight, wherein the amount of said carbon black is from about 100 to about 250 parts by weight and wherein the amount of plasticizer is from about 7 to about 50 parts by weight.
6. 6. A curable rubber composition as described in claim 5, which includes a chlorosulfonated polyethylene elastomer having a chlorine content of about 25% to about 45% by weight having a sulfur content of about 0.25% to about 2% by weight, wherein the amount of the chlorinated polyethylene elastomer is from about 10 parts to about 40 parts by weight per 70 parts by weight of the chlorinated polyethylene elastomer.
7. 7. The cured rubber composition as described in claim 1.
8. 8. The cured rubber composition as described in claim 3, characterized in that the curing agent comprises a peroxide compound.
9. 9. The cured rubber composition as described in claim 5, characterized in that the curing agent comprises a peroxide compound.
10. 10. A hose, hose or a package, which comprises the composition as described in claim 7.
11. 11. A hose, tube or packing, which comprises the composition as described in claim 8.
12. 12. A hose , tube or a package, which comprises the composition as described in claim 9.
13. 13. A hose or tube resistant to transmission fluid which comprises the composition as described in claim 7.
14. 14. A hose or tube resistant to transmission fluid which comprises the composition as described in claim 9.
15. 15. A high heat resistant rubber composition, which comprises: at least one chlorinated polyethylene rubber having about 20% to about 45% chlorine by weight, the total amount of said one or more chlorinated polyethylene rubbers being 70 parts by weight; at least one ethylene-octene copolymer having an octene content of from about 25% to about 55% by weight, the amount of said one or more ethylene-octene copolymers being from about 5 to about 49 parts by weight per 70 parts by weight of said one or more elastomers chlorinated polyethylene; at least one ethylene-acrylic elastomer having a Mooney viscosity of about 10 to about 25 and / or at least one polyacrylic elastomer having a Mooney viscosity of about 10 to about 70, the total amount of said one being or more ethylene-acrylic elastomers and / or polyacrylic elastomers of from about 5 to about 49 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene elastomers; and one or more EPDM rubbers characterized in that the amount of repeating units of ethylene is from about 30% to about 70% by weight, and the amount of repeating units of diene is from about 0.1% to about 8% by weight, and wherein the amount of said EPDM rubber is from about 10 parts by weight to about 50 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene elastomers.
16. 16. A rubber composition resistant to high heat such and as described in claim 15, characterized in that the amount of the ethylene-acrylic elastomer and / or the polyacrylic elastomer is in an amount of about 5 to about 35 parts by weight.
17. 17. A high heat resistant rubber composition as described in claim 16, characterized in that the ethylene-acrylic elastomer has a Mooney viscosity of about 13 to about 19 and wherein the polyacrylic elastomer has a Mooney viscosity. from about 25 to about 55, which includes an antioxidant in an amount of about 0.1 to about 4 parts by weight per 70 parts by weight of said one or more chlorinated polyethylene rubbers, and including carbon black in an amount of about 40 to about 200 parts by weight per 70 parts by weight of the chlorinated polyethylene elastomer.
18. 18. A high heat resistant rubber composition as described in claim 17, characterized in that the chlorinated polyethylene elastomer contains from about 25% to about 40% by weight of chlorine, wherein the amount of octene in said copolymer of Ethylene-octene is from about 35% to about 45% by weight and wherein the amount of the antioxidant is from about 0.5 to about 2 parts by weight and wherein the amount of carbon black it is from about 70 to about 150 parts by weight.
19. 19. A high heat resistant rubber composition as described in claim 18, characterized in that the amount of EPDM rubber is from about 12 to about 35 parts by weight, wherein said ethylene repeat units are from about 35% to about 60% by weight of said EPDM and wherein the amount of repeating diene units is from about 0.2% to about 2% by weight of said EPDM; wherein the amount of said ethylene-octene copolymer is from about 10 to about 20 parts by weight and wherein the amount of said ethylene-acrylic elastomer and / or polyacrylic elastomer is from about 10 to about 30 parts by weight.
20. 20. A high heat resistant rubber composition as described in claim 19, which includes from about 5 to about 49 parts by weight of a chlorosulfonated polyethylene elastomer having from about 25% to about 45% by weight of chlorine and about 0.25% to about 2% by weight of sulfur.
21. 21. The cured rubber composition resistant to high heat as described in claim 15.
22. 22. The cured rubber composition resistant to high heat as described in claim 17, characterized in that said curing agent is a peroxide compound.
23. 23. The cured rubber composition resistant to high heat as described in claim 19, characterized in that the curing agent is a peroxide compound.
24. 24. A hose, tube or packing, which comprises the composition as described in claim 21.
25. 25. A hose, tube or packing, which comprises the composition as described in claim 22.
26. 26. A hose, tube or packing, which comprises the composition as described in claim 23.
27. 27. A hose or packing for transmission liquids, which comprises the composition as described in claim 21.
28. 28. A hose or packing for a transmission fluid, which comprises the composition as described in claim 23.