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    • 专利摘要:
    conveyor belt. The present invention is based on the discovery that neodymium polybutadiene rubber can be built into heavy duty conveyor belts as a conveyor cover layer to greatly improve the wear resistance of the belt. such heavy duty conveyor belts are of particular value for use in mining iron ore, copper ore, coal and other abrasive materials. these belts accordingly offer a longer service life, reduce mine shutdown time, reduce costs, and improve overall mine productivity without imposing adverse effects on employee health or safety, and without adversely impacting the environment. the present invention more specifically describes a conveyor belt which is constituted by a transport cover layer, a reinforcement layer which is situated below the transport cover layer, and a pulley cover layer which is situated below the layer of reinforcement, where the transport cover layer is constituted of neodymium polybutadiene rubber.
    公开号:BR102015001721B1
    申请号:R102015001721-9
    申请日:2015-01-26
    公开日:2021-08-03
    发明作者:Mayu Si；Heng-Huey Yang；Watudura Prabodha Upul Silva；Michael K. Stockdale；Thomas George Burrowes
    申请人:Contitech Usa, Inc；
    IPC主号:
    专利说明:

    field of invention
    [001] The invention relates to conveyor belts that are highly resistant to abrasion and that are particularly useful because of their excellent resistance to abrasion in transporting minerals and coal in mining operations. Fundamentals of Invention
    [002] In a multitude of commercial applications, it is common to employ a heavy duty conveyor belt for the purpose of transporting products and materials. Conveyor belts employed in this way can be relatively long, for example on the order of miles, and represent a costly component to an industrial material handling operation. For example, conveyor belts are widely used to move minerals, coal, and a wide variety of manufactured products from one point to another. Heavy duty conveyor belts used in mining operations can span distances of many miles and represent a high-cost component of an industrial material handling operation. For example, such conveyor belts are often used in typical mining applications to transport minerals below ground in mines as well as above ground.
    [003] Conventional conveyor belts that are used in heavy duty applications are typically comprised of a cured rubber as a top layer, a cured rubber as a bottom layer, and a fabric reinforcing layer (a carcass) that is sandwiched between the top layer and the bottom layer. Conveyor belts used in mining operations can be as large as tens of feet wide and up to about 7.62 cm thick. The main material used in such conveyor belts is generally a rubber-like material or moderately flexible elastomeric material, and the belt is typically reinforced by a plurality of longitudinally extending fabric reinforcements or metallic cables or cords that are positioned within the belt and extend along its length.
    [004] All conveyor belts are obviously susceptible to normal wear and tear in addition to damage to the material being transported and/or other difficult environmental conditions. Unfortunately, conveyor belts that are used in mining operations are particularly susceptible to damage from the material being transported on them, and a tear or cut can develop on the surface of the belt that comes into contact with the material being transported (the conveyor cover surface. of the belt). For example, sharp edges of the material being transported, such as iron ore and copper ore that are particularly abrasive, can dig into the belt surface and this can result in the development of a tear and deeper propagation into the belt body. . Such damage can ultimately result in belt failure. In the event that the conveyor belt suffers catastrophic damage or otherwise becomes inoperable, the costs of repairing the conveyor belt, cleaning up spilled material, and related downtime can be substantial. In any case, a long serviceable view without the need for ongoing maintenance and damage repair is highly desirable from the point of view of cost reduction and efficient use of personnel and equipment.
    [005] Over the years, some improvements have been made to the wear resistance of rubber covered materials used in the manufacture of conveyor belts to convey highly abrasive materials that quickly wear out conventional rubber conveyor belt covers. However, these improvements have generally only been enhanced by virtue of being based on blends of standard general purpose elastomers such as styrene-butadiene rubber (SBR), natural rubber and polybutadiene rubber. Despite these developments, there is still a longstanding need in the mining industry for a premium belt with significantly improved abrasion resistance in order to extend belt life, reduce shutdown time, and improve productivity. It is also important that such an improved conveyor belt retains all other performance characteristics necessary to be commercially viable.
    [006] One approach in achieving improved abrasion resistance is to incorporate a transport layer having improved abrasion characteristics to the conveyor belt. However, it is critical for such a transport cover layer to be able to be embedded in the belt in a manner in which it does not delamination from the belt casing. In other words, it is critical for such an abrasion resistant material used in creating the conveyor cover layer to exhibit good adhesion to the conveyor belt body so that it does not peel over the life of the belt. It is also important that the elastomeric material employed in the transport cover layer is capable of being compounded in a conventional manner and is capable of being processed in conventional rubber processing equipment, thus avoiding major capital expenditures. It is, of course, also important that the material can be used without causing health, safety and/or environmental problems. Invention Summary
    [007] The present invention is based on the discovery that polybutadiene neodymium rubber can be constructed in the form of heavy duty conveyor belts as a conveyor cover layer to greatly improve the wear resistance of the belt. Polybutadiene neodymium rubber can be processed in conventional rubber processing equipment and using conventional formulations and compounding techniques. In any case, conveyor belts for heavy duty applications which have a much improved resistance to surface damage can be made by using polybutadiene neodymium rubber in the transport cover layer. Such heavy duty conveyor belts are of particular value for use in mining iron ore, copper ore, coal and other abrasive materials. These belts offer longer life, reduce mine shutdown time, reduce costs, and improve overall mine productivity without having an adverse effect on worker health or safety, and without causing harmful impacts to the environment.
    [008] The present invention more specifically describes a conveyor belt which is constituted by a transport cover layer, a reinforcement layer which is situated below the transport cover layer, and a pulley cover layer which is situated below the reinforcement layer, where the transport cover layer is made of polybutadiene neodymium rubber. Brief description of the drawings
    [009] Figure 1 is a cross-sectional view of a conveyor belt of this invention having a transport cover layer that is constituted of polybutadiene neodymium rubber, a reinforcement layer that is situated below the transport cover layer, where the layer The reinforcement layer includes three layers of fabric reinforcement, and a pulley cover layer which is situated below the reinforcement layer.
    [010] Figure 2 is a cross-sectional view of a conveyor belt of this invention having a transport cover layer that is constituted of polybutadiene neodymium rubber, a reinforcement layer that is situated below the transport cover layer, where the layer Reinforcement includes steel reinforcement elements, and a pulley cover layer which is situated below the reinforcement layer. Detailed description of the invention
    [011] As illustrated in Figure 1, the heavy duty conveyor belt 1 of this invention includes a transport cover layer 2 which is constituted of polybutadiene neodymium rubber, a reinforcement layer 4 which is situated below the transport cover layer 2, and a pulley cover layer 7 which is situated below the reinforcing layer 4 and which is made of a conventional rubberized polymer. In that embodiment of the invention, the reinforcement layer 4 includes a first fabric reinforcement layer 5A, a second fabric reinforcement layer 5B, and a third fabric reinforcement layer 5C. However, in alternative embodiments of this invention, the reinforcement layer 4 may contain a single fabric reinforcement layer, two fabric reinforcement layers or four or more fabric reinforcement layers.
    [012] Figure 2 illustrates another embodiment of the present invention where the reinforcement layer 4 includes a plurality of steel reinforcement elements 6 that are embedded in the matrix 8 of the reinforcement layer 4. In this embodiment of the invention, the load conveyor belt heavy 1 also includes a transport cover layer 2 which is constituted of polybutadiene neodymium rubber, a reinforcement layer 4 which is situated below the transport cover layer 2 and a pulley cover layer 7 which is situated below the layer. of reinforcement 4 and which is made of a conventional rubberized polymer.
    [013] The neodymium polybutadiene rubber used in the transport cover layer is synthesized using a neodymium catalyst system and is accordingly referred to herein as neodymium polybutadiene rubber. The neodymium catalyst system employed in the synthesis of polybutadiene rubber is normally considered to be a "pseudo-living" catalyst system and the polybutadiene rubber synthesized in its presence normally increases in molecular weight with increasing monomer conversions. Such neodymium catalyst systems are typically comprised of (1) a neodymium compound, (2) an organoaluminum compound, and (3) at least one compound that contains at least one labile halide ion.
    [014] The neodymium compound in the neodymium catalyst system includes a neodymium atom to which bond-type groups or atoms are attached. These compounds are sometimes known as coordination-type compounds and are typically of the structure NdL3, where Nd represents a neodymium atom and where L represents an organic bond. The organic bond which typically contains from 1 to 20 carbon atoms and will typically be selected from (1) o-hydroxyaldehydes, (2) o-hydroxyphenones, (3) aminophenols, (4) hydroxy esters, (5) hydroxy quinolines , (6) beta-diketones, (7) monocarboxylic acids, (8) ortho dihydric phenols, (9) alkylene glycols, (10) dicarboxylic acids, (11) alkylated derivatives of dicarboxylic acids and (12) phenolic esters.
    [015] The organic bonds of the neodymium compound can be monovalent and bidentate or divalent and bidentate. Some representations of such organic bonds or groups include (1) o-hydroxyaldehydes, such as salicylaldehyde, 2-hydroxyl-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde and the like; (2) O-hydroxyphenones, such as 2'-hydroxyacetophenone, 2'-o-hydroxybutyrophenone, 2'-hydroxypropiophenone and the like, (3) aminophenols such as o-aminophenol, N-methyl o-aminophenol, N-ethyl o- aminophenol and the like; (4) hydroxy esters such as ethyl salicylate, propyl salicylate, butyl salicylate and the like; (5) phenolic compounds such as 2-hydroxyquinoline, 8-hydroxyquinoline and the like; (5) β-diketones such as acetylacetone, benzoylacetone, propionylacetone, isobutyrylacetone, valeylacetone, ethylacetylacetone and the like; (7) monocarboxylic acids, such as acetic acid, propionic acid, valeric acid, hexanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, stearic acid, and the like; (8) ortho dihydric phenols, such as pyrocatechol; (9) alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol and the like; (10) dicarboxylic acids, such as oxalic acid, malonic acid, maleic acid, succinic acid, o-phthalic acid, and the like; (11) alkylated derivatives of the dicarboxylic acids described above and (12) phenolic esters such as o-hydroxyanisole, o-hydroxyethyl phenol ether and the like.
    [016] Some representative examples of neodymium compounds that may be used include neodymium acetylacetonate, neodymium naphthenate, neodymium neodecanoate, neodymium octanoate, neodymium tris-salicyaldehyde, neodymium tris-(8-hydroxyquinolate), tris(II- allyl) neodymium chloride, tris(II-allyl) neodymium bromide, tris(II-allyl) neodymium iodide, neodymium tetramethoxide, neodymium tetraethoxide, neodymium tetrabotuoxide, and other neodymium compounds that are complexed with bonds containing 1 to 20 carbon atoms.
    [017] The organoaluminum compound used in the neodymium catalyst system typically contains at least one carbon bond with aluminum and can be represented by the structural formula: i.R2 b.R1 - Al - R3 where R1, R2 and R3 may be the same or different, where R1 is selected from the group consisting of alkyl (including cycloalkyl), alkoxy, aryl, alkaryl, arylalkyl and hydrogen radicals; where R2 is selected from the group consisting of alkyl (including cycloalkyl), aryl, alkaryl, arylalkyl radicals and hydrogen; and where R3 is selected from the group consisting of alkyl (including cycloalkyl), aryl, alkaryl, and arylalkyl radicals. Some representatives of organoaluminum compounds corresponding to that formula include: diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydrate, diphenylaluminum hydride, di-p-tolyaluminum hydride, hydrated dibenzylaluminum, phenylethylaluminum hydride, phenyl-n-propylaluminum hydrate, p-tolyethylaluminum hydride, p-tolyl-n-propylaluminum hydrate, p-tolylisopropylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride and hydride benzylisopropylaluminium and other organoaluminium hydrides. Also included are octylaluminum dihydride, butylaluminum dihydride, isobutylaluminum dihydride, octylaluminum dihydride, amylaluminum dihydride, and other organoaluminum dihydrides. Also included state diethylaluminum ethoxide and dipropylaluminum ethoxide. Also included trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-propylaluminum, trihexylaluminum, ricyclohexylaluminum, trioctylaluminum, triphenylaluminum, triphenylaluminum , ethyl-di-p-tolylaluminum, ethyl-di-p-tolylaluminum, diethylphenylaluminum, diethyl-p-tolylaluminum, diethylbenzylaluminum and other triorganoaluminum compounds.
    [018] The third catalyst component of the neodymium catalyst system is a compound that contains a halide ion. Some examples of halide ions that can be used include bromide ions, chloride ions, fluoride ions, and iodide ions. A combination of two or more of these ions can also be used. These halide ions can be introduced as (1) hydrogen halides; (2) alkyl, aryl, alkaryl, aralkyl and cycloalkyl metal halides where the metal is selected from groups II, III-A and IV-A of the Periodic Table; (3) metal halides from Groups III, IV, V, VI-B and VIII of the Periodic Table and (4) organometallic halides corresponding to the general formula ML(3-y)Xy where M is a metal selected from the group that consists of Group III-B metals of the Periodic Table having atomic numbers from 21, 39 and 57 to 71 inclusive: L is an organic bond containing 1 to 20 carbon atoms and selected from the group consisting of (a) o - hydroxyaldehydes, (b) ao-ahydroxyphenones, (c) hydroxyquinolines, (d) β-diketones, (e) monocarboxylic acids, (f) ortho dihydric phenols, (g) alkylene glycol, (h) dicarboxylic acids, (i) alkylated derivatives of dicarboxylic acids, and (l) phenolic ethers, where X is a halide ion and where y is an integer ranging from 1 to 2 representing the number of halide ions attached to the metal M. The organic bond L can be of monovalent and bidentate or divalent and bidentate form.
    [019] Representative examples of such compounds containing a labile halide ion include (1) inorganic halide acids such as hydrogen bromide, hydrogen chloride and hydrogen iodide; (2) organometallic halides, such as ethylmagnesium bromide, butylmagnesium bromide, phenylmagnesium bromide, methylmagnesium chloride, butylmagnesium chloride, ethylmagnesium iodide, phenylmagnesium iodide, diethylaluminum bromide, diethylaluminum bromide, diisobutylaluminum bromide, diisobutylaluminum bromide, diisobutylaluminum bromide diethylaluminum, ethylaluminum dichloride, ethylaluminum sesquichloride, diisobutylaluminum chloride, isobutylaluminum dichloride, dihexylaluminum chloride, cyclohexylaluminum dichloride, phenylaluminum dichloride, didodecylaluminum chloride, diethylaluminum dibutylaluminum fluoride, diethylaluminum fluoride, dibutylaluminum fluoride, aluminum phenylaluminum diiodide, trimethyltin bromide, triethyltin chloride and the like; (3) inorganic halides, such as aluminum bromide, aluminum chloride, aluminum iodide, antimony pentachloride, antimony trichloride, boron tribromide, boron trichloride, ferric chloride, gallium trichloride, molybdenum pentachloride, phosphorus tribromide , phosphorus pentachloride, stannic chloride, titanium tetrachloride, titanium tetraiodide, tungsten hexachloride and the like; and (4) organometallic halides (Group III-B), such as t-butylsalicylaldehyde (III) chloride, salicylaldehyde (III) chloride, 5-cyclohexylaldehydrocerium (III) chloride, 2-acetylphenolatecerium (III) chloride of oxalate cerium (III), oxalate cerium (III) bromide and the like. Preferred compounds which contain a labile halide ion are inorganic halide acids and organometallic halides.
    [020] The neodymium catalyst system can be prepared using an "in situ" technique or it can be "preformed". By "in situ" is meant that the catalyst components are separately added to the 1,3-butadiene monomer to be polymerized. By "preform" is meant the manner in which the catalyst components are mixed together prior to exposing any of the components to the 1,3-butadiene monomer to be polymerized. It is also known that when employing the type of catalyst system described in this invention, the presence of the monomer is not essential for the formation of a kind of active catalyst, thus facilitating the use of "preformed" catalysts. Furthermore, it is known that newly "preformed" catalysts are often more active than catalysts that might age before use. Highly improved "pre-formed" catalysts can be prepared by carrying out the "pre-form" in the presence of small amounts of 1,3-butadiene monomer. Preformation in the presence of 1,3-butadiene monomer results in homogeneous (soluble) catalyst systems, whereas those prepared by mixing in the absence of 1,3-butadiene monomer are often heterogeneous (insoluble). Such a "preforming" technique is described in detail in U.S. Patent No. 3,794,604 which is incorporated herein by reference.
    [021] The proportions of catalyst components of the neodymium catalyst system used in the polymerization of 1,3-butadiene monomer can vary widely. When the halide ion of the halogen-containing compound is a bromide, chloride, or iodide ion, the atomic ratio of the halide ion to the neodymium meta can range from about 0.1/1 to about 6/1. A more preferred ratio is from about 0.5/1 to about 3.5/1 and the most preferred ratio is about 2/1. However, when the halide ion of the halogen containing compound is fluoride ion, the ratio of fluoride ion to neodymium metal ion ranges from about 20/1 to about 80/1 with the most preferred ratio being about about 30/1 to about 60/1. The molar ratio of trialkylaluminum hydride or alkylaluminum hydride to neodymium metal can range from about 4/1 to about 200/1 with the most preferred range being from about 8/1 to about 100/1. The molar ratio of diolefin to neodymium metal can range from about 0.2/1 to 3000/1 with the most preferred range being from about 5/1 to about 500/1.
    [022] The amount of catalyst loaded into the polymerization system can vary over a wide range: the only requirement being that a catalytic amount of the catalyst composition, sufficient to cause polymerization of the 1,3-butadiene monomer, be present in the system. reaction. Low catalyst concentrations are desirable in order to minimize ash problems. It has been found that polymerizations will occur when the catalyst level of the neodymium metal ranges between 0.05 and 1.0 millimole of neodymium metal per 100 grams of monomer. A preferred ratio is between 0.1 and 0.3 millimoles of neodymium metal per 100 grams of monomer. The concentration of total catalyst system employed, of course, depends on factors such as system purity, the desired polymerization rate, polymerization temperature, and other factors. Therefore, specific concentrations cannot be given except to say what catalytic amounts are used.
    [023] The polymerization of 1,3-butadiene monomer can be carried out by using a volume polymerization procedure or a solution polymerization procedure employing suitable inert solvents. By the term "inert solvent" is meant that the solvent or diluent does not enter the surface of, or adversely affect, the resulting polymer. Such solvents are usually aliphatic, aromatic and cycloaliphatic hydrocarbons, representatives of which are pentane, normal hexane, heptane, toluene, cyclohexane and the like. In many cases, it is desirable to use a solvent that is a mixture of hexane isomers which are often referred to as the "hexanes" solvent. In any case, the solvent/monomer volume ratio can vary over a wide range. Up to a volume ratio of 20 or more to 1 solvent to monomer can be employed. It is usually preferred, or more convenient, to use a solvent to monomer ratio of 3/1 to about 6/1. In bulk polymerization procedures the reaction medium is substantially solvent free and will contain no more than about 10% organic compounds that are solvents for the polymer being synthesized, based on the total weight of the reaction medium. In most cases, the reaction medium will contain less than 4% by weight of solvents or virtually no solvents. Volume polymerization can be carried out in the total absence of solvents.
    [024] The temperature at which the polymerization reaction is carried out can vary over a wide range. Typically, the temperature can range from extremely low temperatures such as -60°C to high temperatures such as 150°C or more. Thus, temperature is not a critical factor that has a substantial effect on the polymerization of 1,3-butadiene monomer in neodymium polybutadiene rubber. It is generally preferred, however, to conduct the reaction at a temperature in the range of about 10°C to about 90°C to obtain a reasonable rate of polymerization and as a matter of convenience. The pressure at which polymerization is carried out can also vary over a wide range. The reaction can be carried out at atmospheric pressure or, if desired, it can be carried out at subatmospheric or superatmospheric pressure. Generally, a satisfactory polymerization is obtained when the reaction is carried out under almost autogenous pressure, developed by the reactants under the operating conditions used.
    [025] The polymerization of 1,3-butadiene rubber with the neodymium catalyst system can be conducted in the presence of a vinyl halide to moderate the molecular weight (Mooney viscosity) of the produced neodymium polybutadiene rubber. Vinyl halides that can be used as molecular weight regulators include vinyl fluoride, vinyl chloride, vinyl bromide, and vinyl iodide. Vinyl bromide, vinyl chloride and vinyl iodide are preferred. Generally, vinyl chloride and vinyl bromide are most preferred. The amount of vinyl halide used will vary with the molecular weight that is desired for the polymer being synthesized. The use of greater amounts of vinyl halide results in the production of a polymer having lower molecular weights. As a general rule of thumb, about 0.05 to 10 phm (parts per hundreds of monomer parts) of a vinyl halide will be used. In most cases from 0.1 phm to 2.5 phm of a vinyl halide will be present during polymerization. Those skilled in the art will be able to easily determine the amount of vinyl halide in order to produce a polymer having a specifically desired molecular weight and resulting Mooney viscosity. A more detailed description of the synthesis of neodymium polybutadiene rubber and the control of its molecular weight is provided in U.S. Patent No. 4,663,405 to Morford Church Throckmorton. The synthesis of neodymium polybutadiene rubber is also described in greater detail in U.S. Patent No. 4,699,960 to Gordini, Carbonaro and Spina. The teachings of U.S. Patent No. 4,663,405 and U.S. Patent No. 4,699,960 are incorporated herein by reference for purposes of describing the polybutadiene neodymium rubber and neodymium catalyst systems and polymerization techniques that can be used in their synthesis.
    [026] Neodymium polybutadiene rubber will have a cis-1,4-microstructure content of at least 96% and will often have a cis-1,4-microstructure content of at least 97% or even 98%. Neodymium polybutadiene rubber will typically have a Mooney ML 1+4 viscosity at 100°C that is within the range of 35 to 65. Neodymium polybutadiene rubber will preferably have a Mooney ML 1+4 viscosity at 100°C that is within the range of range from 35 to 60 and will more preferably have a Mooney ML 1+4 viscosity at 100°C that is within the range of 40 to 50.
    [027] The transport cover layer 2 is typically about 5 mm to 10 mm thick and is constituted of a polybutadiene neodymium rubber. The carrier cover layer can be created exclusively from neodymium polybutadiene rubber or can be a blend of neodymium polybutadiene rubber and one or more other rubberized polymers. The other rubberized polymers that can be included in such blends with the neodymium polybutadiene rubber can be included at levels up to 30 phr (parts by weight per 100 parts by weight of rubber). These additional rubberized polymers are typically selected from styrene-butadiene rubber, natural rubber, synthetic polyisoprene rubber, nitrile rubber, isoprene-butadiene rubber, nickel polybutadiene rubber, styrene-isoprene-butadiene rubber, and ethylene-propylene-diene rubber. It is normally preferred that the additional rubberized polymer is natural rubber or nickel polybutadiene rubber. In either case, the additional rubberized polymer can be included at a level that is within the range of about 1 phr to about 30 phr with the neodymium polybutadiene rubber being present in the carrier cover layer 2 at a level that is within the range of about 70 phr to about 99 phr. If desired, the additional rubber polymer will more typically be included in the carrier cover layer 2 at a level that is within the range of about 5 phr and about 25 phr with the neodymium polybutadiene rubber present at a level that is within from the range of about 75 phr to about 95 phr.
    [028] Natural rubber and/or nickel polybutadiene rubber can be included in the transport cover layer 2 at a level that is within the range of about 2 phr to about 25 phr with the neodymium polybutadiene rubber present in a level that is within the range of about 75 phr to about 98 phr. More typically, natural rubber and/or nickel polybutadiene rubber will be included, if desired, at a level that is within the range of about 5 phr to about 20 phr with the neodymium polybutadiene rubber present at a level which is within the range of about 80 phr to about 95 phr. In cases where natural rubber and/or nickel polybutadiene rubber are included in the transport cover layer, it is typically present at a level that is within the range of about 10 phr to about 15 phr with the rubber of neodymium polybutadiene present at a level that is within the range of about 85 phr to about 90 phr.
    [029] The nickel polybutadiene that can be used in the transport cover layer 2 is synthesized using a nickel catalyst system. The nickel catalyst system is typically made up of (1) an organonickel compound, (2) an organoaluminium compound, and (3) a fluorine-containing compound such as a boron trifluoride, hydrogen fluoride and hydrogen fluoride complexes that are prepared by forming hydrogen fluoride with ketone, an aldehyde, a nitrile, an oxygen-containing mineral acid, an ester, an alcohol, a phenol, or water. The molecular weight of polybutadiene nickel rubber can be controlled by conducting polymerization in the presence of a small amount of olefin selected from the group consisting of 1-butene, isobutylene, cis-2-butene, trans-2-butene and allene . The molecular weight of nickel polybutadiene rubber can also be controlled by conducting polymerization in the presence of para-styrenated diphenylamine. A more detailed description of nickel polybutadiene rubber synthesis is provided by U.S. Patent No. 5,698,643 and U.S. Patent No. 5,451,646. The teachings of U.S. Patent No. 5,698,643 and U.S. Patent 5,451,646 are incorporated herein by reference for purposes of describing nickel polybutadiene rubbers and the synthesis of such nickel polybutadiene rubbers. These nickel polybutadiene rubbers include cis-1,4-polybutadiene rubbers from Budene® 1207, Budene® 1208, and Budene® 1280 high. Budene® 1280 high cis-1,4-polybutadiene rubber which has a high level of branching and which offers impressive processability is highly preferred for use in the transport cover layer 2.
    [030] Nickel polybutadiene rubber will typically have a cis-1,4-microstructure content of at least 96% and will more typically have a cis-1,4-microstructure content of at least 97%. In some cases, nickel polybutadiene rubber will have a cis-1,4-microstructure content of about 98%. For example, nickel polybutadiene rubber can have a cis-1,4-isomer content of about 97%, a trans-isomer content of 2%, and a vinyl content of about 1%. Nickel polybutadiene rubber will typically have a Mooney ML 1+4 viscosity at 100°C that is within the range of about 30 to about 70 and will more typically have a Mooney ML 1+4 viscosity at 100°C that is within the range. from about 35 to about 65. It is typically preferred that nickel polybutadiene rubber has a Mooney ML 1+4 viscosity at 100 Ca that is within the range of about 40 to about 50. Nickel polybutadiene rubber it will also typically have a dilute solution viscosity that is within the range of about 1.8 dl/g to about 2.2 dl/g.
    [031] The transport cover layer 2 will also typically additionally consist of at least one reinforcing filler. The reinforcing filler will normally be carbon black, silica or lignin with carbon black typically being preferred. The filler is typically present at a level that is in the range of 20 phr to 80 phr and is more typically present at a level that is in the range of 30 phr to 75 phr. In most cases, the filler will be present in the transport cover layer 2 at a level that is within the range of 40 phr to 70 phr.
    [032] Virtually any type of carbon black commonly available, and commercially produced, can be used in the practice of this invention. The carbon blacks used in the practice of this invention can be in the form of pellets or a non-pellet flocculating mass. Preferably, for more uniform mixing, non-pellet carbon black is preferred. Carbon blacks having a surface area (EMSA) of at least 20 m 2 /g and more preferably from at least 35 m 2 /g to 200 m 2 /g or more are preferred. The surface area values used in this order are those determined by ASTM test D-1765 using the cetyltrimethyl ammonium bromide (CTAB) technique. Among these useful carbon blacks are furnace blacks, channel blacks, and lamp blacks. More specifically, examples of carbon blacks include super abrasion furnace blacks (SAF), high abrasion furnace blacks (HAF), fast extrusion furnace blacks (FEF), fine furnace blacks (FF), intermediate super abrasion furnace blacks ( ISAF), semi-reinforcement furnace blacks (SRF), medium processing channel blacks, hard processing channel blacks, and conductive channel blacks. Other carbon blacks that can be used include acetylene blacks. Blends of two or more of the above carbon blacks can be employed as reinforcing fillers in the practice of this invention.
    [033] The carbon black used in the transport cover layer will preferably have an STSA surface area that is within the range of about 60 m2/g to 200 m2/g. The carbon black used in the transport cover layer will most preferably have an STSA surface area that is within the range of about 80 m 2 /g to 160 m 2 /g. The carbon black will most preferably have an STSA surface area that is within the range of about 100 m 2 /g to 140 m 2 /g. The carbon black will preferably have an OAN structure that is within the range of 100 cc/100 g to 160 cc/100 g to 145 cc/100 g. In many cases it is preferable to use N121 carbon black in the practice of this invention. Carbon black N121 has an iodine absorption number that is within the range of 114 to 128 g/kg, a DBP absorption number of 124 to 140 10-5 m2/kg, a specific CTAB absorption surface area from 112 to 130 103 m2/kg, an STSA from 105 to 123 103m2/kg, a specific nitrogen absorption surface area of 115-129 103m2/kg, a dye resistance of 111-127%, a maximum loss heat of 3%, a dump density of 280 to 360 kg/m3, and a maximum ash content of 0.5%.
    [034] The transport cover layer 2 may also contain a reinforcing silica. The reinforcing silica filler can be used in the transport cover layer 2 of the conveyor belts of this invention and can also typically be characterized by having an absorption value of dibutylphthalate (DBP) in a range of from about 100 to about 400. and more typically from about 150 to about 300. The reinforcing silica filler typically has an average final particle size that is within the range of 0.01 to 0.05 microns as determined using an electron microscope, although Specific silica particles can be even smaller, and sometimes larger in size. Various commercially available reinforcing silica fillers can be used in the practice of this invention. Some representative examples of such silicas include those from PPG Industries which are sold under the Hi-Sil trademark under the designations 210 and 243, silicas available from Rhone-Poulenc under the designations Z1165MP and Z165GR, and silicas available from Evonik Industries under the designation Ultrasil ® 7000 GR with a BET surface area of approximately 170 m2/g.
    [035] In cases where a reinforcing silica is employed as a filler, a silane coupling agent will also be included at a level that is within the range of 1 phr to about 5 phr. The silica coupling agent will typically be a mercaptosilane, a blocked mercaptosilane, or an organosilicon compound of the general formula: Z-Alk-Sn-Alk-Z (I) where Z is selected from the group consisting of:
    where R1 is an alkyl group containing 1 to 4 carbon atoms, a cyclohexyl group, or a phenyl group; where R2 is an alkoxy group containing from 1 to 8 carbon atoms, or a cycloalkoxy group containing from 5 to 8 carbon atoms; where Alk is a divalent hydrocarbon of 1 to 18 carbon atoms and where n represents an integer from 2 to 8. Blocked mercaptosilanes and mercaptosilanes that can be used in the practice of this invention are described in International Patent Publication No. WO 2006/076670 . The teachings of WO 2006/076670 are incorporated herein by reference for the purpose of describing specific mercaptosilanes and specific blocked mercaptosilanes that can be used in the practice of this invention. The teachings of WO 03091314 are also incorporated herein by reference for purposes of describing specific silanes that can be used in the practice of this invention that emit low levels of volatile organic compounds or non-volatile organic compounds.
    [036] Specific examples of sulfur-containing organosilicon compounds that can be used as silica coupling agent according to the present invention include 3,3'-bis(trimethoxysilylpropyl) disulfite, 3,3'-bis(triethoxysilylpropyl) tetrasuphite, 3,3'-bis(triethoxysilylpropyl) octasulfite, 3,3'-bis(trimethoxysilylpropyl)tetrasulfite, 2,2'-bis(triethoxysilylethyl) tetrasulfite, 3,3'-bis(trimethoxysilylpropyl) trisulfite, 3,3'-bis (triethoxysilylpropyl) trisulfite, 3,3'-bis(tributoxysilylpropyl) disulfite, 3,3'-bis(triethoxysilylpropyl) hexasulfite, 3,3'-bis(trimethoxysilylpropyl) octasulfite, 3,3'-bis(trioctoxysilylpropyl) tetrasulfite, 3 ,3'-bis(triethoxysilylpropyl) disulfite, 3,3'-bis(tri-2"-ethylhexoxysilylpropyl) trisulfite, 3,3'-bis(triisooctoxysilylpropyl) tetrasulfite, 3,3'-bis(tri-t-butoxysilylpropyl) disulfite, 2,2'-bis(methoxy diethoxy silyl ethyl) tetrasulfite, 2,2'-bis(tripropoxysilylethyl) pentasulfite, 3,3'-bis(tricyclonexoxysilylpropyl) tetrasulfite, 3.3 '-bis(tricyclopentoxysilylpropyl) trisulfite, 2,2'-bis(tri-2"-methylcyclohexoxysilylethyl) tetrasulfite, bis(trimethoxysilylmethyl) tetrasulfite, 3-methoxy ethoxy propoxysilyl 3'-diethoxybutoxysilylpropyltetrasulfite, 2,2'-bis(dimethyl) methoxysilylethyl) disulfite, 2,2'-bis(dimethyl sec.butoxysilylethyl) trisulfite, 3,3'-bis(methyl butylethoxysilylpropyl) tetrasulfite, 3,3'-bis(dit-butylmethoxysilylpropyl) tetrasulfite, 2,2'-bis (phenyl methyl methoxysilylethyl) trisulfite, 3,3'-bis(diphenyl isopropoxysilylpropyl) tetrasulfite, 3,3'-bis(diphenyl cyclohexoxysilylpropyl) disulfite, 3,3'-bis(dimethyl ethylmercaptosylylpropyl) tetrasulfite, 2,2'-bis( methyl dimethoxysilylethyl) trisulfite, 2,2'-bis(methylethroxypropoxysilylethyl) tetrasulfite, 3,3'-bis(diethyl methoxysilylpropyl) tetrasulfite, 3,3'-bis(ethyl disec.butoxysilylpropyl) disulfite, 3,3'-bis (propyl diethoxysilylpropyl) disulfite, and 3,3'-bis(butyl dimethoxysilylpropyl) trisulfite, 3,3'-bis(phenyl dimethoxysilylpropyl) tetrasulfite, 3-phenyl et oxybutoxysilyl 3'-trimethoxysilylpropyl tetrasulfite, 4,4'-bis(trimethoxysilylpropyl) tetrasulfite, 6,6'-bis(triethoxysilylhexyl) tetrasulfite, 12,12'-bis(triisopropoxysilyl dodecyl) disulphite, 18,18'-bis(trimethoxysilyl octadecyl) tetrasulfite, 18,18'-bis(tripropoxysilyl octadecenyl) tetrasulfite, 4,4'-bis(trimethoxysilyl-butene-2-yl) tetrasulfite, 4,4'-bis(trimethoxysilylcyclohexylene) tetrasulfite, 5,5'-bis(dimethoxymethylsilylpentyl) trisulfite, 3,3'-bis(trimethoxysilyl-2-methylpropyl) tetrasulfite, 3,3'-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfite.
    The preferred sulfur-containing organosilicon compounds are 3,3'-bis(trimethoxy or triethoxy siliopropyl) sulfites. The most preferred compound is 3,3'-bis(triethoxysilylpropyl) tetrasulfite. Therefore, with respect to formula I, Z is preferably:
    where R2 is an alkoxy of 2 to 4 carbon atoms, with 2 carbon atoms being particularly preferred; Alk is a divalent hydrocarbon of 2 to 4 carbon atoms with 3 carbon atoms being particularly preferred; and en is an integer from 3 to 5 with 4 being particularly preferred.
    [038] The amount of silica coupling agent that should be incorporated into the elastomeric compositions of this invention will vary depending on the level of siliceous fillers that is included in the rubberized composition. Generally speaking, the amount of coupling agent used will range from about 0.01 to about 5 parts by weight per part by weight of siliceous fillers. Preferably, the amount of silica coupling agent used will range from about 0.02 to about 1 part by weight per part by weight of siliceous fillers. Preferably, the amount of silica coupling agent used will range from about 0.04 to about 0.4 part by weight per part by weight of siliceous fillers. More preferably, the amount of silica coupling agent included in the elastomeric compositions of this invention will range from about 0.05 to about 0.25 parts by weight per part by weight of siliceous fillers.
    [039] In order to obtain optimal belt performance characteristics, including the highest levels of abrasion resistance, it is desirable that the rubber formulation used in the conveyor overlay layer include a maximum wax level of 2.0 phr. It is also preferred that the rubber formulation of the transport cover layer includes no more than about 2.5 phr of process aid additives, preferably no more than 1.0 phr of process aid additives, being more It is preferred that the rubber formulation used in the transport cover layer is free of process aid additives. It is also preferred that the transport cover layer includes zinc oxide at a level that is within the range of 2.5 phr to 5 phr, and preferably at a level that is in the range of 2.5 phr to 3.5. phr. In one embodiment of this invention, the rubber formulation used in the carrier cover layer contains less than 0.5 phr of tackifying resins and is preferably devoid of tackifying resins.
    [040] The reinforcement layer 4 is constituted of a fabric or steel reinforcement, such as galvanized steel. The fabric used in the reinforcement layer 4 can be made up of virtually any fabric material having suitable physical properties. For example, the fabric can be a polyester fabric, a nylon fabric, or a polyester and nylon fabric. The fabric is typically coated with a conventional dip resorcinol-formaldehyde-latex (RFL) as it is widely used throughout the tire and industrial rubber products industry for treating fabric reinforcements. U.S. Patent No. 3,525,703 describes a water-based adhesive composition for bonding synthetic fiber material to rubber that may be employed in the practice of this invention. The teachings of U.S. Patent No. 3,525,703 specifically describe the use of styrene-butadiene latex and vinylpyridine-styrene-butadiene latex in such water-based adhesive compositions. The teachings of U.S. Patent No. 3,525,703 are incorporated herein by reference for the purpose of describing a suitable dip formulation.
    [041] A typical RFL dip formulation may contain about 250 to 30 parts by weight of water, 5 to 15 parts by weight of resorcinol, about 10 to 20 parts by weight of formaldehyde, about 0.1 to 0, 5 parts by weight of sodium hydroxide, about 200 to 280 parts by weight of vinyl pyridine latex, and about 8 to 16 parts by weight of ammonia. Such RFL immersion can be done by first preparing a resorcinol-formaldehyde solution by mixing the desired amount of sodium hydroxide (NaOH) in water and then adding the desired amounts of resorcinol and formaldehyde to a basic water solution with constant mixing. Then, the RFL dip solution is created by adding the desired amount of resorcinol-formaldehyde solution in vinyl pyridine latex with the solution being constantly mixed. At that point, the desired amount of ammonia is added with mixing being continued until a homogeneous solution is obtained. The temperature will normally be maintained between about 21°C and 27°C throughout the mixing procedure. RFL dipping can then be used to coat the fabric material which will normally be a woven fabric using conventional procedures.
    [042] The pulley covering layer 6 is situated below the reinforcement layer 4 and is constituted of a conventional rubber. Conventional rubber will typically be styrene-butadiene rubber, natural rubber, synthetic polyisoprene rubber, polybutadiene rubber, polychloroprene rubber, or nitrile rubber (a copolymer of 1,3-bitadiene and acrylonitrile).
    [043] This invention is illustrated by the following examples which are for illustrative purposes only and are not considered to limit the scope of the invention or the form in which it may be practiced. Unless specifically stated otherwise, parts and percentages are given by weight. Table 1

    Ni PBD = nickel polybutadiene rubber Nd PBD = neodymium polybutadiene rubber pli = pounds per square inch.
    [044] As can be seen from Table 1, only the rubber formulation lays with neodymium polybutadiene rubber (Example 1) exhibited good DIN abrasion while maintaining acceptable curing and processing characteristics. In fact, the carrier cover layer formulation exhibited a non-rotating DIN abrasion of less than 25. It should also be noted that this improvement in abrasion resistance was achieved by sacrificing other important physical properties.
    [045] While certain representative embodiments and details have been illustrated for purposes of illustrating the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made here without departing from the scope of the present invention.
    权利要求:
    Claims (20)
    [0001]
    1. Conveyor belt comprising a transport cover layer, a reinforcement layer which is situated below the transport cover layer, and a pulley cover layer which is situated below the reinforcement layer, characterized in that the The carrier cover layer is comprised of 20 phr to 80 phr carbon black, 75 phr to 98 phr neodymium polybutadiene rubber and 2 phr to 25 phr natural rubber, wherein the carbon black consists of carbon black having an STSA surface area that is within the range of 80m2/g to 200m2/g, and wherein the neodymium polybutadiene rubber has a cis-1.4 isomer content of at least 96%.
    [0002]
    2. Conveyor belt according to claim 1, characterized in that the transport cover layer is additionally constituted of at least one additional rubberized polymer selected from the group consisting of styrene-butadiene rubber, polyurethane rubber. synthetic isoprene, nitrile rubber, isoprene-butadiene rubber, nickel polybutadiene rubber, styrene-isoprene-butadiene rubber and ethylene-propylene-diene rubber.
    [0003]
    3. Conveyor belt according to claim 1, characterized in that the additional rubber polymer is nickel polybutadiene rubber.
    [0004]
    4. Conveyor belt according to claim 3, characterized in that nickel polybutadiene rubber has a cis-1.4 isomer content of at least 96 percent.
    [0005]
    5. Conveyor belt according to claim 1, characterized in that the layer of the conveyor cover includes waxes at a level from 0 phr to 2.0 phr.
    [0006]
    6. Conveyor belt according to claim 5, characterized in that the conveyor cover layer includes zinc oxide at a level of which it is in the range of 2.5 phr to 5 phr.
    [0007]
    7. Conveyor belt according to claim 6, characterized in that the conveyor cover layer includes not more than 2.5 phr of auxiliary process additives.
    [0008]
    8. Conveyor belt according to claim 5, characterized in that the conveyor cover layer includes zinc oxide at a level that is in the range of 2.5 phr to 3.5 phr.
    [0009]
    9. Conveyor belt according to claim 8, characterized in that the conveyor cover layer does not include more than about 1.0 phr of auxiliary process additives.
    [0010]
    10. Conveyor belt according to claim 5, characterized in that the transport cover layer is devoid of additives to aid the process.
    [0011]
    11. Conveyor belt according to claim 1, characterized in that the carbon black has an STSA surface area that is within the range of 100 m2/g to 200 m2/g.
    [0012]
    12. Conveyor belt according to claim 1, characterized in that the carbon black has an STSA surface area that is within the range of 100 m2/g to 140 m2/g
    [0013]
    13. Conveyor belt comprising a transport cover layer, a reinforcement layer which is situated below the transport cover layer, and a pulley cover layer which is situated below the reinforcement layer, characterized in that the The carrier cover layer is comprised of neodymium polybutadiene rubber and nickel polybutadiene rubber, wherein the nickel polybutadiene rubber is present at a level which is in the range of from about 2 phr to about 25 phr and where the Neodymium polybutadiene rubber is present at a level that is in the range of about 75 phr to about 98 phr.
    [0014]
    14. Conveyor belt according to claim 13, characterized in that the nickel polybutadiene rubber has a cis-1,4 isomer content of about 97%, a trans-isomer content of about 2% and a vinyl content of about 1% and wherein the nickel polybutadiene rubber has a Mooney ML 1+4 viscosity at 100°C that is in the range of about 30 to about 70;
    [0015]
    15. Conveyor belt according to claim 14, characterized in that the nickel polybutadiene rubber has a dilute solution viscosity that is in the range of about 1.8 dl/g to about 2.2 dl/g.
    [0016]
    16. Conveyor belt comprising a transport cover layer, a reinforcement layer which is situated below the transport cover layer, and a pulley cover layer which is situated below the reinforcement layer, characterized in that the The carrier cover layer is comprised of 20 phr to 80 phr carbon black, 75 phr to 98 phr neodymium polybutadiene rubber, and 2 phr to 25 phr natural rubber, wherein the neodymium polybutadiene rubber has a cis-1.4 isomer content of at least 96 percent, and wherein the carbon black is N121 carbon black with an iodine absorption number that is within the range of 114 g/kg to 128 g/kg, a DBP absorption number that is within the range of 124 x 10-5 m2/kg to 140 x 10-5 m2/kg, a CTAB absorption specific surface area that is within the range of 112 x 103 m2/ kg to 130 x 103 m2/kg, an STSA that is within the range of 105 x 103 m2/kg to 123 x 103 m2/kg, a surface area ie specific nitrogen absorption which is within the range of 115 x 103 m2/kg to 129 x 103 m2/kg, a hue strength which is within the range of 111% to 127%, a leakage density which is within the range of 280 kg/m3 360 kg/m3, and a maximum ash content of 0.5%.
    [0017]
    17. Conveyor belt according to claim 16, characterized by the fact that the transport cover layer is devoid of process aid additives.
    [0018]
    18. Conveyor belt according to claim 16, characterized in that the transport cover layer is devoid of adhesive resins.
    [0019]
    19. Conveyor belt according to claim 16, characterized in that the carbon black is present at a level that is within the range of 35 phr to 75 phr.
    [0020]
    20. Conveyor belt according to claim 16, characterized in that the carbon black is present at a level that is within the range of 40 phr to 70 phr.
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    同族专利:
    公开号 | 公开日
    AU2015200422B2|2019-02-28|
    CA2878816A1|2015-07-31|
    CL2015000245A1|2015-09-25|
    CN105111528A|2015-12-02|
    IN2015DE00215A|2015-08-07|
    BR102015001721A2|2017-05-30|
    MX367003B|2019-08-02|
    CA2878816C|2020-11-03|
    AU2015200422A1|2015-08-20|
    ZA201500624B|2016-01-27|
    US20150217940A1|2015-08-06|
    US9580249B2|2017-02-28|
    MX2015001447A|2015-07-30|
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    法律状态:
    2017-05-30| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2017-09-19| B25F| Entry of change of name and/or headquarter and transfer of application, patent and certif. of addition of invention: change of name on requirement|Owner name: VEYANCE TECHNOLOGIES, INC. (US) |
    2018-01-16| B25D| Requested change of name of applicant approved|Owner name: CONTITECH USA, INC. (US) |
    2018-10-30| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-02-18| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-06-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/01/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201461934569P| true| 2014-01-31|2014-01-31|
    US61/934,569|2014-01-31|
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