Methods of producing an elastomer compound and elastomer compounds

专利摘要:
Methods to prepare elastomer compounds are described that include dry mixing at least one additive to an elastomer composite masterbatch at low temperatures over a shortened mixing cycle with reduced energy consumption. The elastomer composite masterbatch is produced in a liquid masterbatch process. The resulting elastomer compounds are further described as well as property improvements that can be achieved.
公开号:ES2784531A2
申请号:ES202090015
申请日:2018-11-08
公开日:2020-09-28
发明作者:David Reynolds；Gerald D Adler；Martin C Green
申请人:Cabot Corp；
IPC主号:

专利说明:

[0004] The present invention relates to methods for making or preparing elastomer composites from masterbatches of elastomer composites.
[0005] Many commercially important products are made up of elastomeric compositions in which the particulate filler is dispersed in any of several synthetic elastomers, elastomer or natural rubber blends. Carbon black (abbreviated here as CB), for example, is widely used as a reinforcing agent in natural rubber and other elastomers. It is common to produce a masterbatch, i.e., a filler premix, elastomer, and various optional additives, such as extender oil, and then in some cases to mix such masterbatch with additional elastomer in a subsequent mixing step.
[0006] The carbon black masterbatch is prepared with different grades of carbon black available on the market that vary both in surface area and per unit of weight and structure, which describes the size and complexity of the carbon black aggregates formed. by the fusion of primary carbon black particles with each other. Numerous commercially important products are formed from such rubber-dispersed carbon black particulate filler elastomeric compositions. Such products include, for example, vehicle tires in which different elastomeric compositions can be used for the tread portion, sidewalls, wire mesh and carcass. Other products include, for example, engine mounting bushings, weatherstripping, hoses, windshield wipers, and other automotive components; off-road vehicle rolling elements; aerospace components comprising rubber compounds; anti-vibration bushings, gaskets and components for vehicles, buildings, marine facilities, ships and aircraft; seals, gaskets, hoses, belts, liners, shoes, wheels, conveyors, and other industrial systems, for example, for conveying mineral ores during processing, and the like.
[0007] Good dispersion of carbon black in rubber compounds has been recognized for some time as one of the most important objectives for good quality and consistent product performance, and a considerable effort to develop procedures to evaluate the quality of dispersion in rubber. Mixing operations have a direct impact on mixing efficiency and macro dispersion. In general, better macrodispersion of carbon black in a dry mixed masterbatch is achieved by longer mixing and more intensive mixing. Unfortunately, however, by achieving better macrodispersion for a longer time, a more intense mix degrades the elastomer in which the carbon black is dispersed. This is especially problematic in the case of natural rubber, which is highly susceptible to mechanical / thermal degradation, and in the case of higher surface area CB, particularly those that have a relatively low structure. Longer and more intensive mixing, using known mixing techniques and apparatus, such as an internal mixer, reduces the molecular weight of the natural rubber masterbatch composition. Thus, it is known that the improved macrodispersion of carbon black in natural rubber is achieved with a corresponding, generally undesirable reduction in the molecular weight of the rubber.
[0008] In addition to dry mix techniques, it is known to continuously feed latex and a suspension of carbon black to a stirred coagulation tank. Such "wet" techniques are often used with synthetic elastomer, such as styrene butadiene rubber (SBR). The coagulation tank contains a coagulant such as salt or an aqueous acidic solution that typically has a pH of about 2.5 to 4. The latex and carbon black suspension are mixed and coagulated in the coagulation tank into small beads. (usually a few millimeters in diameter) called wet crumbs. The crumb and acid effluent are separated, typically by means of a vibrating screen or the like. The crumb is dumped into a second stirred tank where it is washed to achieve a neutral or near neutral pH. Subsequently, the crumb is subjected to additional vibrating sieving and drying steps and the like. Variations on this method have been suggested for the coagulation of natural and synthetic elastomers, for example, in US Patent No. 4,029,633 commonly owned by Hagopian and US Patent No. 3,048,559 to Heller. Additional wet masterbatch methods are described in, for example, US Patent No. 6,841,606, PCT Publication WO 2006/068078, and PCT Publication WO 2006/080852. As used herein, "wet mix" or "wet masterbatch" techniques refer to methods in which the elastomer latex or synthetic rubber solution is combined in liquid form with slurry fluid. particulate filler to produce an elastomer composite material.
[0009] The resulting elastomeric composite is referred to as a wet mix or wet masterbatch composite. Instead, dry mix composites are prepared by dry mix methods in which the dry particulate filler is combined with dry rubber.
[0010] An alternative mixing method is disclosed in commonly owned U.S. Patent Nos. 6,048,923 and 6,929,783, which disclose a wet masterbatch process in which separate streams of a slurry of black are combined. carbon and an elastomeric latex under conditions in which the elastomeric latex coagulates without the use of added coagulants. The masterbatch is dehydrated to about 15% to 25% water content and then passed through a continuous mix and optionally an open mill. An additional method of dewatering and drying a wet masterbatch to optimize the microdispersion of the resulting elastomer composite is described in United States Patent Application Publication No. US 2011/0021664.
[0011] Dry masterbatch chewing (for example, after it is produced by a dry mix process or a wet masterbatch process, followed by drying) can be used to adjust the Mooney viscosity and improve processability while incorporates additives such as oils, antioxidants, and zinc oxide. Vulcanizing agents (curing agents) can also be added or can be added in a second chewing step. However, the mixing step performed with the present vulcanizing agents may need to be performed at lower temperatures (eg, below 120 ° C) to avoid precure. Also, overmixing can be detrimental to viscoelastic properties and can increase flocculation during storage, which can increase storage hardening and further degrade rubber performance (Wang, et al., KGK Kautschuk Gummi Kunststoffe, Vol. 7-8, 2002, pp. 388-396). Therefore, it is desirable to have methods for combining vulcanizing agents with elastomer composites produced by a wet masterbatch method that do not compromise the mechanical properties of the resulting vulcanizate.
[0012] For some applications, it is desirable to employ elastomer blends to optimize the mechanical properties of the masterbatch and / or a vulcanized rubber product from the masterbatch. Blends can be produced by cocoagulating a mixture of elastomer webs (see, for example, US Patent No. 4,271,213) or by recovering a polymer blend from a mixture of elastomer latex and a solution containing a second polymer (See, for example, US Patent No. 5,753,742. Alternatively, elastomer blends can be produced by dry mixing two elastomers together. It is known to blend dry mixed elastomer composites with additional elastomer to reduce hysteresis.
[0013] Mabry et al., US Patent No. 7,105,595 B2, incorporated herein by reference in its entirety, describes elastomer composite blends prepared by wet / dry mixing methods and apparatus. In the wet mix step, for example, the elastomer composite is prepared by the wet masterbatch method described in US 6048923. The coagulum produced by such a wet mix step, with or without intermediate processing steps, then it is mixed with additional elastomer in a dry mix step, for example, during compounding to form elastomer composite blends. The additional elastomer combined with the coagulum may be the same or different from the elastomer (s) used in the wet mix step.
[0014] The dry mix (composition) of elastomer composite masterbatches produced by wet masterbatch techniques introduces all hazards to material properties that were originally avoided by wet mixing the elastomer composite masterbatch; however, dry mixing one or more additives with a masterbatch is beneficial for a myriad of reasons including, but not limited to, introducing additional elastomer (s), filler (s), antioxidant (s), oils, curing agent (s) and the like. Generally, this dry mixing step is performed in a two-stage mix or one-stage mix. The general common belief in the rubber industry is that this dry mixing of additional additives in the elastomeric composite to form an elastomeric composite should be done at temperatures of at least 130 degrees C and for a sufficient duration to generate good dispersion. of the filler in the elastomer composite or elastomer composite material, to generate good chemical interaction with the elastomer and filler, and / or generate bonded rubber. This common belief held for elastomer composite masterbatches formed by dry or wet masterbatch methods. However, for wet masterbatches, this post-dry mixing of one or more additives at temperatures of at least 130 degrees C may be unnecessary and / or detrimental to product performance, as such temperatures can degrade the properties of the rubber compound. and / or product performance. The present invention addresses this problem with an efficient method of dry mixing additives into materials. elastomer compounds formed by wet masterbatch methods.
[0015] DESCRIPTION OF THE INVENTION
[0016] This invention addresses the problem (s) described above in view of the discovery that high temperatures, such as 130 degrees C or higher, should be avoided during dry mixing of the elastomer composite masterbatch with a or more additives to form an elastomer compound. The use of temperatures below 130 degrees C during the dry mix step or process can prevent degradation of one or more properties of the elastomeric compound and / or preferably, improves one or more of these properties, while unexpectedly allowing the use of shorter mix cycles and lower energy consumption to achieve equivalent or higher elastomer compound and rubber article properties.
[0017] Accordingly, the present invention relates to a method for producing an elastomeric composite, wherein the method includes preparing an elastomeric composite masterbatch from a wet masterbatch method (for example, from elastomer latex slurry and particulate filler slurry), and then dry mix (in a one-stage mix or two or more stage mix) the elastomer composite masterbatch with at least one additive to obtain an elastomer compound such that during dry mixing, the process temperature for one-stage mixing is maintained at a process temperature of less than 130 degrees C, and for two-stage mixing, it is maintained at a process temperature less than 130 degrees C in stage one of the two stage mix and does not exceed 120 degrees C in stage two of the two stage mix when at least one curative is used in stage two. If no curative is used in stage two, then stage two of the two stage mix can optionally be kept at a temperature of less than 130 degrees C.
[0018] The present invention further relates to elastomeric compounds and vulcanized elastomeric compounds made from the processes of the present invention.
[0019] Furthermore, the present invention relates to articles that incorporate or are manufactured from the elastomeric compounds of the present invention, including, but not limited to, vehicle tire treads, sidewalls, wire mesh, and carcass; off-road vehicle rolling elements; engine mounting bushings, conveyor belts, windshield wipers and other automobile components comprising rubber compounds; components aerospace comprising rubber compounds, anti-vibration components for vehicles, buildings, marine facilities and aircraft; seals, gaskets, hoses, belts, liners, shoes, wheels and conveyors for transporting mineral ores and the like.
[0020] Advantageously, in some of the implementations disclosed herein, product attributes such as the mechanical strengthening and / or hysteresis properties of the elastomer compound are maintained or improved with the methods of the present invention, relative to the standards. while the methods of the present invention unexpectedly conserve process time and energy.
[0021] In the alternative, or in addition, the reinforcing properties, such as the ratio of the tensile modulus at 300% and 100% strain, are maintained or improved over elastomeric compounds prepared in accordance with the present invention.
[0022] Certain elastomer compounds of the present invention may have superior properties such as, for example, with respect to hysteresis and / or reinforcement, compared to elastomer compounds produced by the same wet masterbatch technique but with dry mix of the additive. so that the process temperature is at least 130 degrees C during the initial, non-productive dry mix stage.
[0023] The above and other features of the invention include various details of construction and combinations of parts, and other advantages, will now be more particularly described with reference to the accompanying drawings and will be indicated in the claims. It will be understood that the particular method and device embodying the invention are shown by way of illustration and not as a limitation of the invention. The principles and features of this invention can be employed in various and numerous implementations without departing from the scope of the invention.
[0024] BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figures 1-3 are graphs representing the results achieved for the low temperature dry mix (the present invention) and the high temperature dry mix (comparative) as set forth in Example 1. Figure 1 is a graph showing a property comparison, i.e. Tan Max delta at 60 degrees C versus the data from the M300 / M100 module. Figure 2 is a graph showing Tan Max delta at 60 degrees C as a function of the process temperature used in the first stage of the dry mix. Figure 3 is a graph showing the properties of M300 / M100 depending on the process temperature used in the first stage of the dry mix.
[0026] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0027] The present invention generally relates to methods for producing elastomeric compounds and the resulting elastomeric compounds.
[0028] In the methods of the present invention for producing an elastomeric composite, in general, the methods comprise, consist essentially of, consist of, or include preparing or providing an elastomeric composite masterbatch and then dry mixing (in one step or two or more stages) the elastomeric composite masterbatch with at least one additive to obtain an elastomeric composite so that during dry mixing, the process temperature for one-step mixing is at a temperature below 130 degrees C and for two-stage mixing, it is below 130 degrees C in stage one of two-stage mixing and does not exceed 120 degrees C in stage 2 of two-stage mixing when at least one curative in stage 2. If no curative is used in stage 2 (ie a non-productive mixing step), then stage 2 of the two-stage mixing can optionally be lower than 130 degrees C. If the dry mix takes place in more than two stages, such as three-stage dry mix, then generally, for any dry mix stage before the last stage, the process temperature of the dry mix is less than 130 degrees C and the process temperature of the mix Last stage (productive) dry generally does not exceed 120 degrees C. If no curative is used in the last stage, then all stages of multi-stage mixing can optionally be kept below 130 degrees C. When two or more dry mix stages are used, only the addition of at least one additive has to happen in at least one of the stages. Thus, when two or more stages are used, one of the dry mix stages can be a dry mix of the elastomer composite masterbatch or the material obtained from a pre-dry mix stage with no added additive. Alternatively, when two or more dry mix stages are used, two or more dry mix stages may have an additive added during each dry mix stage, where the additive may be the same or different from a previous dry mix stage. For the purposes of the present invention, the dry mixing stages or steps are carried out at a temperature below 130 degrees C, and if at least one dry mixing stage reaches a process temperature of 130 degrees C, then it is considered dry mix at high temperature and is not part of the present invention.
[0029] In more detail, and as used herein, the elastomer composite masterbatch is a masterbatch obtained by "wet mix" or "wet masterbatch" or "liquid masterbatch" techniques. Elastomer composite masterbatch refers to masterbatches formed from methods in which the elastomer latex or synthetic rubber solution is combined in liquid form with particulate fill suspension fluid to produce the elastomeric composite. elastomer, and other processes that employ liquid or solvent to more easily disperse reinforcing materials in an elastomer-containing fluid to form an elastomer composite masterbatch. The resulting elastomeric composite can be referred to as a wet mix or wet masterbatch composite. Instead, "dry-mix" masterbatches or composites are prepared by dry-mix methods in which the dry particulate filler is combined with dry rubber, or a dry elastomeric masterbatch and the filler is combined with elastomer and / or additional filler, and / or a second dry masterbatch to make a compound.
[0030] The elastomeric composite masterbatch used in the methods of the present invention can further be characterized as having sufficient bound rubber present prior to any mixing or dry processing. Bound rubber formation generally refers to adsorption of polymer chains to the filler surface (eg, adsorption of polymer chains of an elastomer latex onto carbon black or other particulate filler). When sufficient bonded rubber is present in a reinforced elastomeric composite, such materials are characterized by favorable Mooney viscosity values (for example, a target Mooney value of about 70 to 80 (ML 1 + 4 @ 100 ° C) for materials comprising approximately 50 phr of filler; with acceptable values of approximately 65 to 90, depending on the formulation of the material). Such Mooney values are correlated with benefits including negligible fill flocculation, lower storage hardening, and good masterbatch processability in downstream manufacturing operations. Thus, the amount of energy applied to work such materials during the production of the elastomeric composite masterbatch is selected to create bonded rubber and produce materials that have such favorable Mooney values in an uncured state.
[0031] The elastomer composite masterbatch (prior to the dry mix step) used in the methods of the present invention may, in addition, or as alternatively, further characterized as having a percentage of non-dispersed infill areas of 10% or less, such as 7% or less, or 5% or less, or 3% or less, or 2% or less, or 1% or less , or 0.5% or less, such as from about 0% to 10%, 0.001% to 10%, 0.01% to 10%, or 0.01% to 5%; or greater than or equal to 1% and less than 10%, or greater than or equal to 1% and less than 8%. This can be measured by an optical microscopy method to quantify the filler macrodispersion in elastomer, such as the method and equation described in column 3 of US6048923B1, to quantify the undispersed carbon black filler particles of at least 10 microns in a larger dimension, or by alternative optical imaging methods to quantify non-dispersed infill in rubber, such as the method for measuring infill scattered areas (i.e., Z-value scattering; expressed as the percentage area of scattered infill ), as disclosed in Otto, et al., New Reference Value for the Description of Filler Dispersion with the Dispergrader 1000 NT, KGK Kautschuk Gummi Kunstoffe 58. Jahrgang, n. 7-8 / 2005; or in ISO 11345, second edition, 2006-02-01, Dispersion evaluation method.
[0032] The elastomer compound of the present invention, as used herein, is an elastomer compound that is the result of dry-mix composition of an elastomer composite masterbatch obtained by "wet-mix" techniques. "or" wet masterbatch "or" liquid masterbatch "with at least one additive (for example, one or more elastomer (s), filler (s) and / or other additives).
[0033] More details, including optional details of the elastomeric composite masterbatch and the resulting composite are provided herein.
[0034] As for the dry mix, this can be one or multiple stages or steps. As noted, the dry mix of the elastomer composite masterbatch and the at least one additive is produced such that the process temperature during dry mix of the elastomer composite masterbatch is kept below 130 degrees C when not used or curative (s) not present. When a curative is used in a productive mix stage, then the process temperature generally does not exceed a process temperature of 120 degrees C during that dry mix stage or any subsequent dry mix stage. Process temperature is a reference to an instrument temperature reading provided by rubber mixing equipment. In general, the maximum temperature of the target process is referred to as the " dump. "The instrument temperature reading is generally based on a thermocouple installed in the mixing chamber wall that continuously records the temperature on the mixing chamber wall. Therefore, the process temperature, as used herein, is a reference to this instrument temperature reading at the instrument's maximum dump temperature. Temperature can be measured using a thermocouple or thermistor, resistance thermometer (RTD), a pyrometer, or any other temperature reading device used in industry that tends to be an accessory in a rubber mixer. The process temperature during the dry mix of the invention is kept below 130 ° C. The more specific process temperature ranges and the combination of the process temperature ranges with the number of stages can be as follows:
[0035] A: For one-step dry mix of elastomer composite masterbatch with at least one additive and provided the additive is not a curing or curing agent: A process temperature below 130 degrees C or not higher than 120 degrees C, such as remaining in a process temperature range of approximately 80 degrees C to 129 degrees C, or approximately 90 degrees C to 129 degrees C, or 100 degrees C to 125 degrees C, or 90 degrees C at 127 degrees C, or 80 degrees C to 120 degrees C, or 90 degrees C to 120 degrees C, or 100 degrees C to about 120 degrees C.
[0036] B: For one-stage dry mix of elastomer composite masterbatch with at least one additive where at least one of the additives is a curative or curing agent: a process temperature not to exceed 120 degrees C, or not to exceed 115 degrees C, such as remaining in a process temperature range of approximately 80 degrees C to 120 degrees C, or approximately 90 degrees C to 120 degrees C, or 80 degrees C to 120 degrees C, or 90 degrees C to 115 degrees C, or 100 degrees C to about 115 degrees C, or 80 degrees C to 110 degrees C.
[0037] C: For the two-stage dry mix of the elastomer composite masterbatch with at least one additive in one or both stages (with the additive being the same or different per stage if used) and provided that the additive is not a curative or curing agent in any of the stages. Dry Mix Stage 1: A process temperature is less than 130 degrees C, or not more than 125 degrees C, or not more than 120 degrees C, such as staying in a process temperature range of about 80 degrees C to 129 degrees C, or about 80 degrees C to 125 degrees C, or about 90 degrees C to 129 degrees C, or 80 degrees C to 120 degrees C, or 90 degrees C to 120 degrees C, or 100 degrees C to about 120 degrees C;
[0038] and, Stage 2 of the dry mix: a process temperature is less than 130 degrees C, or not greater than 120 degrees C, such as remaining in a process temperature range of about 80 degrees C to 129 degrees C, or about 90 degrees C to 129 degrees C, or 125 degrees C, or 80 degrees C to 120 degrees C, or 90 degrees C to 120 degrees C, or 100 degrees C to about 120 degrees C.
[0039] D: For the two-stage dry mix of the elastomer composite masterbatch with at least one additive in one or both stages (with the additive being the same or different per stage if used) and where the additive is used in step 2 and one of the additives in step 2 includes or is a curative or curing agent, and step 1 does not include a curative or curing agent. Next, Stage 1 of the dry mix: a process temperature is less than 130 degrees C, or not more than 125 degrees C, or not more than 120 degrees C, such as staying in a process temperature range of about 80 degrees C to 129 degrees C, or about 80 degrees C to 125 degrees C, or about 90 degrees C to 129 degrees C, or 80 degrees C to 120 degrees C, or 90 degrees C to 120 degrees C, or 100 degrees C to about 120 degrees C; and, Stage 2 of the dry mix: a process temperature that does not exceed 120 degrees C, or that does not exceed 115 degrees C, such as remaining in a process temperature range of approximately 80 degrees C to 120 degrees C, or approximately 90 degrees C to 120 degrees C, or 80 degrees C to 120 degrees C, or 90 degrees C to 115 degrees C, or 100 degrees C to approximately 115 degrees C, or 80 degrees C to 110 degrees C.
[0040] E: For multi-stage dry mix (3 or more dry mix stages) of the elastomer composite masterbatch with at least one additive in one of the stages (with the additive being the same or different per stage if used in 2 or more stages) and where one of the additives in the last stage includes or is a curative or curing agent, and the previous stages do not include a curing or curing agent. Then, any stage before the last stage of the dry mix (the production stage): a process temperature is less than 130 degrees C, or not higher than 120 degrees C, such as staying in a process temperature range of about 80 degrees C to 129 degrees C, or about 90 degrees C to 129 degrees C, or 80 degrees C to 125 degrees C, or 90 degrees C to 125 degrees C, or 80 degrees C at 120 degrees C, or 90 degrees C to 120 degrees C, or 100 degrees C to about 120 degrees C; and, the last stage of the dry mix: a process temperature that does not exceed 120 degrees C, or that does not exceed 115 degrees C, such as remaining in a process temperature range of approximately 80 degrees C to 120 degrees C , or approximately 90 degrees C to 120 degrees C, or 80 degrees C to 120 degrees C, or 90 degrees C to 115 degrees C, or 100 degrees C to approximately 115 degrees C, or 80 degrees C to 110 degrees C.
[0041] The curing or curing agent, for example, can be sulfur and / or an accelerator. To achieve dry mix, any commercially available dry mixer or dry mix technique can be used. Suitable rubber mixing equipment includes closed or internal mixers or extruders equipped with interleaved or tangential rotors and open mixers such as rolling mills, and the operation of the equipment and the process can be performed in batch mode, continuous mode or semi-continuous mode. For example, the mixer used for dry mixing can be of any tangential or interleaved design or a combination thereof, a continuous mixer, an internal mixer, a twin screw extruder, a single screw extruder, or a laminator. Suitable devices are well known and commercially available, including, for example, a Unimix continuous mixer and an MVX (Mixing, Venting, eXtruding) machine from Farrel Corporation of Ansonia, Conn., A long continuous mixer from Pomini, Inc. , a Pomini continuous mixer, interleaved and rotating twin-rotor extruders, non-interleaved double-rotor counter-rotating extruders, Banbury mixers, Brabender mixers, interleaved-type internal mixers, kneader-type internal mixers, continuous compound extruders, the extruder biaxial grinding machine produced by Kobe Steel, Ltd., and a Kobe continuous mixer.
[0042] The temperature of the elastomer composite masterbatch can be controlled during dry mixing with at least one additive, so that the elastomer composite masterbatch does not reach the process temperature of 130 degrees C (or other process temperature highest) during dry mixing, by setting or adjusting one or more of the following parameters: the rpm or mixing speed of the mixer used, the mixing time, using a cooling jacket on the mixer or part of it, using heat sinks or other heat removal devices, adjusting the volume of the elastomer composite masterbatch being mixed, or any combination of these parameters. For example, a lower rpm (or decrease in rpm) of the mixer or mixing paddle or rotor (s) results in lower temperatures of the composite material. Using shorter mix times or using staggered mixes (eg mix, stop, mix, stop, etc.) will control the temperature. As an option, a temperature probe or other temperature monitoring device can be connected to a control box so that one or more of the parameters mentioned herein can be controlled to avoid exceeding the maximum desired temperature. For example, such a control box can be configured so that the mixer rpm is reduced when reaching a maximum temperature or a temperature close to the maximum temperature.
[0043] For the purposes of the dry mix step (s), the additive (s) may be added to the elastomer composite masterbatch in the mixer, or the elastomer composite masterbatch may be added to the additive in the mixer, or both the additive and the elastomer composite masterbatch can be added to the mixer at or near the same time. Any sequence or order can be used and is not critical to achieving the benefit (s) of the present invention. Mixing or blender can be started with the elastomer composite masterbatch alone and / or the additive, and then the other component added thereafter.
[0044] As for the types of additives, one or more additives can be used. If two or more additives are used, the additives can be added at the same time, or in sequence or in any order during dry mixing. More than one mixing stage (and / or mixing device or technique) can be used to add different additives. Additives used with elastomer composites are well known to those skilled in the art and include, for example, one or more of: fillers (eg, carbon black, silica, dual phase carbon silica fillers, black carbon coated silica, metal oxides), elastomers, antioxidants, antiozonants, plasticizers, processing aids (e.g., liquid polymers, oils, and the like), resins, flame retardants, extender oils, lubricants, curing agents, or any combination of any of them. Exemplary additives include, but are not limited to, natural rubber, butadiene rubber, synthetic rubber, additional filler, zinc oxide, or stearic acid, or any combination thereof. The amounts of the additives used vary according to the type of additive used. For example, if the additive is a filler, the amount may be about 1 phr to about 65 phr or more. If the additive is an elastomer, the amount can be from about 5 phr to about 80 phr or more. If the additive is an antioxidant, antiozonant, plasticizer, processing aid (eg, liquid polymers, oils, and the like), resin, flame retardant, extender oil, lubricant, additional filler, and / or curing agent, individual amounts may be from about 0.1 phr to about 5 phr or the combined amounts can be from about 0.1 phr to about 20 phr or more, such as from about 0.1 phr to about 30 phr (phr may be a reference to the material elastomer masterbatch compound). If the at least one additive added to the dry mix is one or more additional filler (s), the additional filler (for example, a second filler, or a mixture of fillers) may be the same or different from the first filler present. in the elastomer composite masterbatch.
[0045] If the at least one additive added to the dry blend is one or more elastomer (s), the additional elastomer (for example, the second elastomer) may be the same or different from the elastomer (for example, the first elastomer) present in the blend. elastomer composite material mother. As used herein, the "first elastomer" or the "second or additional elastomer material" can be a single elastomer or a mixture of elastomers. The second elastomer material can include additional ingredients, such as filler or antioxidant or other additives. For the purposes of the present invention, the elastomeric composite masterbatch in which the particulate filler in the first elastomer is disposed may be referred to as a "pure elastomeric composite masterbatch". The mixture of the pure elastomer composite masterbatch with the optional second elastomer material may be referred to as "elastomer composite blend" during processing or "elastomer composite" in final form.
[0046] As a specific example and as an option, a process for producing an elastomer composite of the present invention may include preparing an elastomer composite masterbatch comprising natural rubber and a first filler filler of carbonaceous aggregate filler (e.g., a reinforcing or semi-reinforced carbon black having an STSA of at least 25 m2 / g, or at least 90 m2 / g, or at least 120 m2 / g), with the option of the first filler charge being al minus about 20 phr, or from about 20 phr to about 150 phr, by a wet masterbatch method; and through mixing or compounding by dry mix, the elastomer composite masterbatch with a second elastomer composite comprising one elastomer and an optional particulate filler to produce an elastomer composite having an optional second filler charge, the second charge of filler is at least about 5 phr.
[0047] As an option, the elastomer compound of the present invention may have a M300 / M100 of the vulcanized elastomer compound that is at least 0.09, or at least 0.2 or at least 0.5 greater than M300 / M100 for a vulcanized elastomer compound of the same composition but prepared where the dry mix step (or one of the dry mix steps) occurred at a temperature equal to or greater than 130 degrees C, such as 140 degrees C or 150 degrees C.
[0048] The elastomeric compounds of the present invention can be curative-free compositions, curative-bearing compositions, or vulcanized rubber materials and products formed from such compositions. Mechanical properties are measured on vulcanized compositions; therefore, after the formation of the wet masterbatch and the dry mix with at least one additive, the resulting elastomeric compound is vulcanized to measure stress and hysteresis properties.
[0049] In certain implementations, the present invention relates to an elastomer composite in which the elastomer composite masterbatch and / or elastomer composite contain particulate filler, eg, carbon black, in an amount of at least about 10 phr, such as, for example, from about 30 phr to about 75 phr, from about 35 phr to about 60 phr, from about 40 phr to about 80 phr. One skilled in the art will recognize that the desired carbon black loading will depend on the surface area and structure of the carbon black. For example, the desired loading for a carbon black that has a surface area, measured by STSA, greater than 120 m2 / g may be much less than the desired loading for a carbon black that has a much lower surface area, such as a carbon black of type N774 (STSA = 29 m2 / g) in some composites, whereas the reverse may be desired in other composites. The present invention improves the dispersion and use of carbon blacks that have a larger surface area, such as N100 and N200 grades of reinforcing carbon blacks, which tend to be difficult to disperse in elastomers using standard industrial mixing processes, and enables or enhances the dispersion and use of carbon blacks having a high surface area in combination with a relatively low structure, for For example, carbon blacks with a STSA surface area in the range of 110 to 230 m2 / g and a COAN structure in the range of 55 to 95 ml / 100 g.
[0050] In certain implementations, the present invention relates to an elastomer compound, and an elastomer compounding process, wherein a first elastomer compound masterbatch made by a liquid masterbatch process is composed, in a mixing process. dry, with a second elastomer masterbatch additive, or with multiple masterbatch additives, at a temperature of less than 130 degrees C. The second elastomer masterbatch additive can be a masterbatch made by a liquid masterbatch process , or it can be a masterbatch made by a dry masterbatch process. The second elastomeric masterbatch additive may comprise the same or different filler (s), and the same or different elastomer (s) as used in the first elastomeric composite masterbatch. For example, the first elastomer composite masterbatch may comprise natural rubber and carbon black, while the second masterbatch additive may comprise butadiene rubber and carbon black, or butadiene rubber and silica, or natural rubber and silica, and / or silica and carbon black, manufactured by a liquid masterbatch process, or combinations thereof. The second masterbatch additive may comprise natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), or isoprene rubber (IR), or modifications or combinations thereof, in any filler combination. , small and elastomers, and can be made in any dry or liquid masterbatch process. Any combination of two masterbatches, one of which is made by a liquid masterbatch process, can be mixed together in the compounding process of the invention to achieve a desired final compound. For example, a compound made from two or more masterbatches may contain 20 to 75 phr of filler, or 30 to 60 phr of filler, or 30 to 50 phr of filler, or 10 to 60 phr of filler, or 10 to 40 phr. filler, and a ratio of two or more elastomers, for example, NR: BR or NR: SBR, or NR / BR + SBR, or NR: IR, or BR: NR, or SBR: NR or IR: NR or others elastomer combinations, 50:50, or 40:60, or 30:70, or 20:80, or 10:90, or 5:95, or any ratio within these ranges.
[0051] Either combining "pure" elastomer composite masterbatch with curatives, antioxidants and / or other small volume ("small") additives, or using a larger amount of additive, such as an additional elastomer, or a second filler reinforcement, or both, or a second masterbatch additive, in the reduced temperature compounding process of the invention, the masterbatch mix of Elastomer composite material with said additives can be carried out by mixing in reduced times and with a reduced energy input, and / or with minimal pre-chewing of the pure elastomer composite material masterbatch. By remaining non-productive, compound mixing stage temperatures below 130 degrees C, stage one mixing time can be significantly reduced, for example, by 10-60%, or 10-50%, or 15 -40%, or 10-30%, or 15-20%, and the applied energy can be reduced, for example, by 10-50%, or 10-30%, or 10-40%, or 15-40%, while achieving at least equivalent, and in some cases, improved mechanical and dynamic properties in the mixed composite comprising the elastomeric composite masterbatch obtained by a liquid masterbatch process. In one implementation, the one-stage mixing is selected to incorporate all the ingredients of the curative package, including the curatives themselves, in a single mixing step. This can be followed by limited amounts of chewing the compound, for example by lamination or extrusion.
[0052] Certain implementations of the elastomer masterbatch, blends and compounds, methods and apparatus for producing them are disclosed below. While various preferred implementations of the invention may employ a variety of different fillers and elastomers, certain parts of the following detailed description of aspects of the method and apparatus of the invention, in some instances, for convenience, describe elastomer composites comprising natural rubber and carbon black and / or silica. It will be within the ability of those skilled in the art, given the benefit of this disclosure, to employ the method and apparatus disclosed herein in accordance with the principles of operation described herein to produce pure elastomeric composites and elastomer composite blends comprising various alternative or additional elastomers, fillers and other materials.
[0053] As noted, the elastomer composite masterbatch is prepared by a wet masterbatch method (for example, from a fluid-containing elastomer, such as a latex or polymer in solution and a suspension of particulate filler) .
[0054] Examples of wet masterbatch processes that can be used herein include those disclosed in US Patent Nos. 6,048,923; 6,929,783 and 8,586,651, the contents of which are incorporated herein by reference and are described below. In such processes, carbon black or other filler is mixed with aqueous fluid to form a suspension that has a concentration of 10-25% by weight of filler and the suspension is fed to a mixing zone of a pressurized clot reactor so that the suspension is jetted into the mixing zone at a speed adjusted to achieve final filler load levels in an elastomer and achieve desired production speed. Natural rubber latex having a dry rubber content of about 20-35% is fed to the mixing zone. The latex flow rate is adjusted to reach the final fill loading levels. The filling suspension and latex are mixed by drawing the latex into the filling suspension in the mixing zone of the clot reactor. During the entrainment process, the filler is intimately mixed with the latex and the mixture coagulates as it exits the mixing zone in a continuous or semi-continuous process. A continuous coagulum or masterbatch crumb is discharged from the coagulum reactor and dried to about 10-20% by weight moisture with a dewatering extruder. The dried coagulum is fed to a continuous mixer and chewed to achieve a moisture content of less than 5% by weight, followed by further chewing, cooling and drying in an open laminator, further cooling, cut into small compressed strips to form a bullet and "loose" product packaging. Other examples of wet masterbatch processes that can be used herein include those disclosed in, for example, US Patent Nos. 5,763,388, 6,841,606, 6,646,028, 7,101,922, 3,335,200 and 3,403,121, and publications US2009 / 062428, WO2011 / 034589, WO2011 / 034587, and United States Patent Publication Nos. 2011/00221664, WO2012 / 037244 and WO2017 / 011548 (the content of which is incorporated herein for reference) and other wet masterbatch processes known to those of skill in the art. In general, an elastomer-containing fluid and a particulate suspension fluid are combined, and the elastomer-containing fluid coagulates to form a masterbatch crumb. The masterbatch crumb may be dried to form a desiccated coagulum, and then worked to form a dry elastomer composite masterbatch with suitable rubber properties for further processing into finished rubber compounds and articles. In certain cases, additives such as curatives, antioxidants, and other "little" additives can be added at a controlled temperature of less than 120 degrees C continuously or semi-continuously to an in-process elastomer composite masterbatch after said intermediate material has dried, and during or after drying, but before packaging, for example, the additives can be mixed into said intermediate material in a laminator and / or with an extruder or low speed mixer located downstream of a dewatering operation. As a consequence of such additions to the intermediates, the storage hardening of the uncured elastomer composite masterbatch can be minimized, and subsequent mixing of the masterbatch with the filler additive and / or the elastomeric additive or blend The mother to make a final compound can be carried out at a temperature below 130 degrees C in one stage, or in a reduced number of stages in relation to industry standards, in less mixing time and with less energy input. In this way, a more uniform dispersion of such additives in the final compound, a more efficient compounding process and better product qualities can be achieved. Such introduction of additives to intermediate materials is particularly useful in the liquid masterbatch processes described in US Patent Nos. 6,048,923; 6,929,783 and 8,586,651.
[0055] Examples of other wet masterbatch processed products that may benefit from this invention include those mentioned in WO 2017 / 103519A1, WO 2017 / 103518A1, WO2017 / 103495A1, WO2017 / 021219A1, WO2016 / 106408A1, WO2016 / 166483A1, WO2016 / 180693A1, WO2012 / 080109A1, WO2012 / 080111A1, WO2013 / 060857A1, WO2013 / 087657A1, US Patent Nos. 9,611,380, 9,670,332, 9,751,992, 7,960,466, 9,758,627, 9,834,658 and 7,932,307, and United States Patent Application Publication Nos. US2018 / 0179343A1, US2018 / 0179303, US2018 / 0230276A1, US2016 / 0185921A1, and US2016 / 0289398A1, the contents of which are incorporated herein by reference.
[0056] As an alternative wet masterbatch technique, the wet rubber masterbatches are made in a process having a step (a) of dispersing the carbon black in the dispersing solvent to produce a suspension solution containing carbon black, a step (P) of mixing the suspension solution containing carbon black with the rubber latex solution to produce a solution of rubber latex containing carbon black, and a step ( ^y ) of solidifying / drying the rubber latex solution containing carbon black. When the carbon black is dispersed in the dispersing solvent, at least a part of the rubber latex solution is added thereto, thereby producing the carbon black-containing suspension solution in which the rubber latex particles are adhere to the carbon black, and step (P) is a step (P- (a)) of mixing the suspension solution containing carbon black, in which the rubber latex particles adhere to the carbon black , with the rest of the latex solution of rubber to produce the carbon black containing rubber latex solution in which the rubber latex particles adhere to the carbon black. In step (P- (a)), the suspension solution is mixed with the remainder of the rubber latex solution to produce a rubber latex solution containing carbon black in which the rubber latex particles adhere to carbon black. The method for mixing the suspension solution with the rest of the rubber latex solution is not particularly limited, and it may be a method for mixing the suspension solution with the rest of the rubber latex solution, using a ordinary dispersing machine, such as high shear mixer, high shear mixer, homomixer, ball mill, bead mill, high pressure homogenizer, ultrasonic homogenizer, or colloid mill. As required, the entire dispersion machine or some other mixing system can be heated at the time of mixing. Afterwards, the rubber latex solution containing carbon black solidifies. The method for solidification may be a method of adding a solidifier to the rubber latex solution containing carbon black, in which the rubber latex particles adhere to the carbon black, to produce a solidified product. The solidifier can be a substance normally used to solidify a rubber latex solution, for example an acid such as formic acid or sulfuric acid, or a salt such as sodium chloride. After the solidification step, the solution containing the solidified product is dried to produce each of the wet rubber masterbatches A and B. The method for drying the solution containing the solidified product may be a method using a machine drying that can be of various types, such as an oven, a vacuum dryer or an air dryer.
[0057] In another alternative process for making the wet masterbatch or elastomer composite masterbatch, the method may include a step of mixing a natural rubber latex with a slurry comprising water and a carbon black dispersed in the same. Ten to 100 parts by weight of the carbon black are mixed with 100 parts by weight of a natural rubber component in the natural rubber latex. For example, a natural rubber field latex can be diluted to 20% rubber content or other amount with deionized water. To dilute natural rubber field latex, an anionic surfactant and alkaline protease can be added. The mixture can be stirred, for example at 40 ° C for eight hours, whereby the amide bonds in the natural rubber field latex were cut. For the suspension of carbon black, a mill can be used colloidal and deionized water and one of several carbon blacks can be loaded into the suspension. The mixture is stirred to form the suspension. For coagulation, the latex and carbon black suspension are loaded into a homomixer. While each mixture is stirred, an acid such as formic acid is added to the mixture until the mixture has reached pH 4.5 or another pH. A coagulated masterbatch is then recovered from the mixture, cleaned with water, and dried until its water content is reduced, for example, to about 40%. The masterbatch is then dried.
[0058] Suitable elastomer-containing fluids include natural and synthetic elastomer latexes and latex blends. The latex must be appropriate for the selected wet masterbatch process and the purpose or application of the final rubber product. It is within the ability of those skilled in the art to select the appropriate elastomeric latex or a suitable combination of elastomeric latex for use in the methods and apparatus described herein, given the benefit of this disclosure.
[0059] Exemplary elastomers for elastomeric latex and / or as an optional additive include, but are not limited to, rubbers, polymers (eg, homopolymers, copolymers, and / or terpolymers) of 1,3-butadiene, styrene, isoprene, isobutylene, 2 , 3-dialkyl-1,3-butadiene, where the alkyl can be methyl, ethyl, propyl, etc., acrylonitrile, ethylene, propylene, and the like. The elastomer can have a glass transition temperature (Tg), as measured by differential scanning calorimetry (DSC), ranging from about -120oC. at approximately 0oC. Examples include, but are not limited to, styrene-butadiene rubber, butadiene rubber, natural rubber, and its derivatives, such as epoxidized natural rubber, chlorinated rubber, polybutadiene, polyisoprene, poly (styrene-co-butadiene), and their derivatives, and extended oil compositions comprising any of them. Mixtures of any of the above can also be used. The latex can be in an aqueous carrier liquid. Particularly suitable synthetic rubbers include: copolymers of from about 10 to about 70 percent by weight of styrene and from about 90 to about 30 percent by weight of butadiene such as copolymer of 19 parts of styrene and 81 parts of butadiene, a copolymer of 30 parts of styrene and 70 parts of butadiene, a copolymer of 43 parts of styrene and 57 parts of butadiene and a copolymer of 50 parts of styrene and 50 parts of butadiene; polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, polychloroprene, and the like, and copolymers of such dienes conjugated with a monomer containing an ethylenic group copolymerizable with them, such as styrene, methyl styrene, chlorostyrene, acrylonitrile, 2-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, Allyl substituted acrylates, vinyl ketone, methyl isopropenyl ketone, methyl vinyl ether, alphamethylene carboxylic acids and their esters and amides such as acrylic acid and dialkylacrylic acid amide. Furthermore, copolymers of ethylene and other high alpha olefins such as propylene, 1-butene and 1-pentene are suitable for use in the present invention. As further noted below, the rubber compositions may contain, in addition to the elastomer and filler, a coupling agent and, optionally, various processing aids, oil extenders, and antidegradants.
[0060] Examples of natural rubber webs include, but are not limited to, field latex, latex concentrate (produced, for example, by evaporation, centrifugation, or cremation), latex skim (for example, the supernatant that remains after production of latex concentrate by centrifugation) and mixtures of two or more of these in any proportion. The latex must be appropriate for the selected wet masterbatch process and the purpose or application of the final rubber product. The latex is typically provided in an aqueous liquid vehicle. Selection of a suitable latex or combination of webs will be within the ability of those skilled in the art given the benefit of the present disclosure and knowledge of generally well recognized selection criteria in the industry.
[0061] Natural rubber latex can also be chemically or enzymatically modified in some way. For example, it can be treated to chemically modify or reduce various non-rubber components, or the rubber molecules can be modified with various monomers or other chemical groups such as chlorine. Exemplary methods of chemical modification of natural rubber latex are disclosed in European Patent Publication Nos. 1489102, 1816144 and 1834980, in Japanese Patent Publication Nos. 2006152211,2006152212, 2006169483, 2006183036, 2006213878, 2006213879, 2007154089 and 2007154095, in US Patents Nos. 6841606 and 7312271, and in US Patent Publication No. 2005-0148723. Other methods known to those of skill in the art may also be employed.
[0062] The particulate filler present in the elastomeric composite masterbatch and / or used as an additive during dry blending may be carbonaceous aggregate particles, for example carbon black, silicone coated or silicone treated carbon blacks, silica, or any combination or mixture of two or more of these. Exemplary carbon blacks include ASTM N100 series - N900 series carbon blacks, for example, N100 series carbon blacks, N200 series carbon blacks, N300 series carbon blacks, N300 series carbon blacks, N500 series, N600 series carbon blacks, N700 series carbon blacks, N800 series carbon blacks, or N900 series carbon blacks. Carbon blacks sold under the trademarks Regal®, Black Pearls®, Spheron®, Sterling® and Vulcan® available from Cabot Corporation, the trademarks Raven®, Statex®, Furnex® and Neotex® and the CD and HV lines available from Birla Carbon (Columbian Chemicals,) and the Corax®, Durax®, Ecorax®, and Purex® trademarks and the CK line available from Evonik (Degussa) Industries, and other fillers suitable for use in rubber or pneumatic applications, they can also be exploited for use with various implementations. Suitable chemically functionalized carbon blacks include those described in WO 96/18688 and US2013 / 0165560, the disclosures of which are incorporated herein by reference. Mixtures of any of these carbon blacks can be used.
[0063] The elastomer composite masterbatches or the elastomer composite may contain carbon blacks having a statistical thickness surface area (STSA, ASTM Standard D6556) of at least about 15 m2 / g, for example, from about 15 m2 / g to about 240 m2 / g, for example, from about 35 m2 / g to about 230 m2 / g, from about 50 m2 / g to about 200 m2 / g, from about 60 m2 / g to about 180 m2 / g, from about 100 m2 / g to about 200 m2 / g.
[0064] Carbon blacks having any of the above surface areas can also have a structure, depending on the oil adsorption number for compressed carbon black (COAN, ASTM D3493), from about 50 to about 115 ml / 100 g, for example, from about 65 to about 75 ml / 100 g, from about 60 to 95 ml / 100 g, from about 75 to about 85 ml / 100 g, from about 85 to about 95 ml / 100 g, from about 95 to about 105 ml / 100 g, or from about 105 to about 115 ml / 100 g.
[0065] The materials described herein as silicon treated carbon blacks are not limited to carbon black aggregates that have been coated or otherwise modified. They can also be a different type of aggregate that has two phases. One phase is carbon, which will still be present as crystallite graphite and / or amorphous carbon, while the second phase is silica (and possibly other silicon-containing species). Therefore, the species phase that contains silicon from silicon-treated carbon black is an intrinsic part of the aggregate; it is distributed in at least a part of the aggregate. Cabot Corporation offers a variety of silicon treated blacks under the name Ecoblack ™ and they are described in more detail in US6028137. It will be appreciated that multiphase aggregates are quite different from the aforementioned silica-coated carbon blacks, which consist of preformed monophasic carbon black aggregates having silicon-containing species deposited on their surface. Such carbon blacks can be surface treated to place a silica functionality on the surface of the carbon black aggregate as described in, for example, US Patent Nos. 6,929,783, 6,541,113 and 5,679. 728.
[0066] As noted above, additives can be used, and in this regard, coupling agents useful for the coupling of silica or carbon black can be useful with silicon-treated carbon blacks. Carbon blacks and many other particulate fillers suitable for use in elastomer compositions, such as silica, zinc oxide, aluminum oxide, other metal oxides, calcium carbonate, and other particulate materials, are commercially available and are known to those of skill. in the matter. For example, precipitated silica fillers in any form, such as highly dispersible granules (HDS), non-HDS granules, silica aggregates, and silica particles; colloidal silica; fumed silica; and any combination thereof, can be used, with or without coupling agents present, in wet masterbatch compositions and / or as an additional filler in the dry mix process. This silicon dioxide or silicon dioxide coated particles may have been chemically treated to include functional groups attached (attached (eg, chemically attached) or adhered (eg, adsorbed)) to the surface of the silica. Examples of suitable grades of HDS include Perkasil® GT 3000GRAN silica from WR Grace & Co, Ultrasil® 7000 silica from Evonik Industries, Zeosil® 1165 MP and 1115 MP silica from Solvay SA, Hi-Sil® EZ 160G silica from PPG Industries, Inc ., and Zeopol® 8741 or 8745 silica from JM Huber Corporation. Examples of suitable grades of conventional precipitated silica (non HDS) include Perkasil® KS 408 silica from WR Grace & Co, Zeosil® 175GR silica from Solvay SA, Ultrasil® VN3 silica from Evonik Industries, Hi-Sil® 243 silica from PPG Industries, Inc. and Hubersil® 161 silica from JM Huber Corporation. Examples of suitable grades of hydrophobic precipitated silica include Agilon®400, 454 or 458 silica from PPG Industries, Inc. and Coupsil® silicas from Evonik Industries, for example Coupsil® 6109 silica.
[0067] One or more additives may also be premixed, if appropriate, with the particulate slurry or elastomer-containing fluid, or as indicated may be combined with the elastomer composite masterbatch during the dry mix step of the present invention. . Other premixes can be used. In one implementation, a liquid elastomer composite masterbatch comprising carbon black is blended in dry form with a second elastomer masterbatch, i.e., one comprising silica filler. By introducing silica filler into a separately produced masterbatch, the silica filler can be dry blended with an elastomer, for example NR, BR, SBR or IR, up to a temperature of at least 130 ° C, to optimize properties dynamic and mechanical reinforcement of the silica filler in the second elastomer composite material. Subsequently, the low-temperature composition of the elastomer composite masterbatch with such a silica masterbatch allows optimization of the dynamic and mechanical reinforcing properties of the silica and other fillers in the composite made from these two mixtures. mother. These mixing steps are most beneficial in composites comprising at least 10 phr of silica filler and at least 30 phr of carbon black. Alternatively, the second elastomeric composite material containing silica filler can be produced in a liquid masterbatch process, such as the processes disclosed in US10,000,612, US9,260,594 and US9,988,502, which are incorporated herein. document by reference.
[0068] In one implementation, the wet masterbatch crumb or clot is passed from a clot reactor of the type described in US6,929,783 to a dewatering extruder through a simple gravity drop or other suitable apparatus known to those skilled in the art. in technique. The dewatering extruder can bring the elastomer composite from, for example, about 70-85% water content, to a desired water content, for example, about 1% to 25% water content, for example, from about 8 to about 25% water content or from about 10 to about 20% water content. The optimum water content may vary with the elastomer used, the type of filler, and the desired downstream processing procedure. Suitable dewatering extruders are well known and commercially available from, for example, the French Oil Mill Machinery Co. (Piqua, Ohio, USA).
[0069] As an exemplary summary, the composite masterbatch of elastomer may comprise:
[0070] i) combining a first fluid comprising elastomer latex with a second fluid comprising particulate filler;
[0071] ii) causing the elastomer latex to coagulate, thereby forming a masterbatch crumb; Y
[0072] iii) drying the elastomer composite masterbatch (eg, to obtain the masterbatch crumb).
[0073] Drying, as an option, may comprise reducing the water content of the masterbatch crumb thereby forming a dehydrated clot; subjecting the desiccated clot to mechanical energy, causing the desiccated clot to heat up as a result of friction, while allowing the desiccated clot, for example, to reach a temperature of about 130 oC to about 190 oC, where the content of water is reduced from about 0.5% to about 3% and wherein substantially all of the decrease in water content is achieved by evaporation, thus producing a chewed masterbatch; and subjecting the chewed masterbatch to at least an additional 0.3 MJ / kg of mechanical energy while further reducing the water content as described in US 8,586,651.
[0074] The elastomeric composite masterbatch may further include, prior to dry blending, chewing the elastomeric masterbatch composite, such as for 30-60 seconds. As an example, chewing may comprise mixing the elastomeric masterbatch composite in an internal mixer, such as a 70-85% fill factor for 30 to about 60 seconds.
[0075] As indicated, the at least one additive can be a curative package or at least one curing agent. To vulcanize the elastomer compound, the added curative package may include a crosslinking agent, necessary activators and accelerators, antioxidants, and additional optional additives, such as various additional processing aids, oil extenders, wax, and antidegradants. When sulfur is used as a crosslinking agent, typical accelerators include zinc oxide and / or stearic acid, and typical activators include sulfenamides such as N-tert-butyl-2-benzothiazole sulfenamide (TBBS) and N-cyclohexyl-2- benzothiazole sulfonamide (CBS). Antioxidants include N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine (6PPD) and those listed in WO2012 / 037244. Other curatives used in rubber processing are peroxides, crosslinkers for urethane, metal oxides, acetoxysilane compounds, and so on. Additional suitable components for sulfur-based and other crosslinking systems are well known to those of skill in the art.
[0076] As an example, in a compounding step (which may be the dry mixing step), the additives, with the exception of sulfur or other accelerating and crosslinking agent, are combined with the pure elastomer composite in a mixing apparatus ( non-curatives are often collectively referred to as "small"). The most common mixing apparatus is the internal mixer, for example the Banbury or Brabender mixer, with interleaved or tangential technology, but other mixers, such as extruders, can also be employed. After that, in a second mixing step, the crosslinking agent is added, for example sulfur and accelerator (if necessary) (collectively referred to as curatives). The second mixing stage is often carried out in the same type of apparatus as the first mixing stage, but can be carried out in a different type of mixer or extruder or in a laminator. One skilled in the art will recognize that once curatives have been added, vulcanization will begin once the proper activation conditions for the crosslinking agent are reached. Therefore, when using sulfur, it is important to keep the temperature below the cure temperature during mixing.
[0077] In one implementation, when the additive includes an additional elastomer, the elastomer composite wet masterbatch employs NR latex, while the second elastomer material introduced during dry mix is butadiene rubber (BR), styrene rubber. butadiene (SBR) or isoprene rubber (IR). With respect to proportions, the BR, IR or SBR additives may be present in the elastomer compound in an amount of from about 5 to about 50% by weight, for example, from about 5% to about 10%, from about 10% to about 20%, from about 20% to about 30%, from about 30% to about 40%, or from about 40% to about 50%, or from about 20% to 80% of the total elastomer in the elastomer composite.
[0078] Regarding the properties of the elastomer compound, the modulus ratio of certain vulcanized elastomer compounds of the present invention may be at least about 5% higher, for example, from about 10% to about 12%, from about 12% to about 15%, or about 15% to about 17% greater than that of a compound of vulcanized elastomer having the same composition but produced by dry mixing with the addition of the same additive at a temperature of at least 130 degrees C. Alternatively, or in addition, the modulus ratio can be at least 0.25 greater or at least 0, 5 major, preferably, at least about 0.75 major, more preferably, at least about 1 major, for example, up to about 2.2 major, up to about 2 major, up to about 1.75 major, or up to about 1.5 greater, than the modulus ratio for a vulcanized elastomer compound having the same composition but produced by dry mixing with the addition of the same additive at a temperature of at least 130 ° C.
[0079] The M300 / M100 ratio (also referred to as "modulus ratio" herein) provides an indication of rubber reinforcement. For carbon black filled vulcanizates, the given elongation stresses reflect, among other things, the effect of filler morphology (particle size and structure) and surface activity, which determines the filler-polymer and aggregate-aggregate interaction. . The ratio of tension at 300% elongation to 100% elongation, M300 / M100 (also known as T ³⁰⁰ / T ¹⁰⁰ ) provides a useful approach to quantify the degree of polymer-filler interaction because the factors that govern the stresses at different elongations are different. Without wishing to be bound by theory, it is presently understood that, at least in certain preferred implementations, the elastomeric compound produced by the wet / dry method described herein is a multi-phase composition. The degree of intermixing of the two phases and the degree to which the boundary layers between the two phases are more or less distinct will depend on numerous factors including, for example, the mutual affinity of the first elastomer and the second elastomeric material, the relative affinity of the filler (s) with one or more of the elastomers, the level of particulate filler, the choice of the particulate filler (s), the relative weight ratio of the first elastomer and the second elastomer material, the effectiveness of the mixing of the pure elastomer composite material and the second elastomer material, etc.
[0080] The elastomeric compound produced by the present invention can be used in the manufacture of rubber articles, including, but not limited to, a vehicle tread, sidewall, wire mesh component, or tire carcass, or engine mount. , bushing, conveyor, belt, anti-vibration device, or windshield wiper, or a seal, gasket, hose, liner, or vehicle wheel or running gear.
[0081] The present invention includes the following aspects / embodiments / features in any order and / or in any combination: The present invention may include any combination of these various features or embodiments above and / or below as set forth in sentences and / or paragraphs. Any combination of features described herein is considered part of the present invention and no limitation is intended on the combinable features.
[0082] EXAMPLES
[0083] Materials and methods
[0084] Unless otherwise indicated below, all times are in seconds and percentages by weight.
[0085] Wet masterbatch methods
[0086] Preparation of the carbon black suspension
[0087] Dry carbon black (N134) (Cabot Corporation, Boston, MA) was mixed with water and ground to form a slurry having a concentration of approximately 16%. The suspension was fed to a mixing zone of a clot reactor as shown in Figures 2-4 and 7 of US 6,929,783 by a homogenizer equipped with a Homogenization Valve at an operating pressure of about 3000 psig, so that the slurry was jetted into the mixing zone of a clot reactor as a finely ground slurry of carbon black. The flow rate of the carbon black slurry was adjusted to about 1200-2500 kg / hr to modify the final carbon black loading levels and achieve the desired production rate. Actual levels of carbon black loading were determined by nitrogen pyrolysis or thermogravimetric analysis (TGA). Specific CB grades and charges are specified in the examples below.
[0088] Natural rubber latex supply
[0089] The field latex having a dry rubber content of about 27-31% was pumped into a mixing portion of a clot reactor configured in a manner similar to that shown in Figures 2-4 and 7 of US6,929,783. The latex flow rate was adjusted between approximately 1000-2500 kg / h to modify the final levels of carbon black loading.
[0090] Carbon black latex mix
[0091] The suspension of carbon black and latex were mixed by drawing the latex into the suspension of carbon black in the mixing zone of the clot reactor. During In the stripping process, the carbon black was intimately mixed with the latex and the mixture coagulated.
[0092] Desiccation
[0093] The masterbatch crumb was discharged from the clot reactor at a rate of between 500 and 1000 kg / hr (dry weight) and dried to approximately 10-20% humidity with a dewatering extruder (The French Oil Machinery Company, Piqua , OH) as illustrated in Figure 1 and described in the text of US6,929,783. In the extruder, the master crumb was compressed and the water squeezed out of the crumb was expelled through a slotted barrel of the extruder.
[0094] Drying
[0095] The dried coagulum was dropped into a continuous mixer (Farrel continuous mixer, rotors # 7 and # 15; 280-320 rpm (FCM), Farrel Corporation) where it was chewed and mixed with 1-2 phr of antioxidant ( 6PPD) in a process described in US8,586,651. The moisture content of the chewed masterbatch coming out of the FCM was around 1-2% and the temperature was between 140 and 180 oC. The product was further chewed, cooled and dried in an open mill. The product was further cooled on a cooling conveyor and cut into small strips, which were compressed together, to form a "loose" bale of product.
[0096] Mix and cure
[0097] The elastomer composite masterbatch bales were opened and the masterbatch compounded according to the formulation in Table 1 and the procedures outlined in Table 2. The amounts of unfilled rubber masterbatch and total rubber were such that the final compound comprised 50 phr of carbon black.
[0098] Table 1
[0103] * N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine
[0104] ** N-cyclohexyl-2-benzothiazole sulfenamide
[0105] Table 2 ("Stage 2") Low T process
[0106]
[0108]
[0110] Table 2 "Eta a 2" High T process
[0111]
[0115] Mixing in one stage ("Stage 1")
[0116] Unless otherwise specified, compounds designated as compounds by a one-step mixing procedure were combined using the formulation in Table 1 and the procedure in Table 3 below.
[0117] Table 3
[0122] Vulcanization was carried out in a press heated to 150 ° C for a time determined by a conventional rubber rheometer (ie, T90 10% of T90, where T90 is the time to achieve a vulcanization of 90%).
[0123] Properties of filled compositions
[0124] The M300 and M100 tensile properties of the vulcanized samples were measured according to ASTM D-412. The relation of the modulus is the relation of M300 / M100, that is, the ratio of the material stress at 300% and 100% strain. Tan delta 60o was determined using a dynamic strain scan between 0.01% and 60% at 10 Hz and 60 ° C. Tan 5max was taken as the maximum value of tan 5 within this range of deformations.
[0125] Example 1
[0126] This example was performed to study the effects of the composition (dry mix) of an elastomer composite masterbatch manufactured by a liquid process at low temperature, that is, less than 130 degrees C ("low T" process), compared to dry mix at higher temperatures, ie 130 degrees C and above ("high T" process). The temperature of Stage 2 when used was always below 120 degrees C for the high T and low T examples, as curatives they were used in Stage 2.
[0127] As shown in the data below, in Table 4, the modulus ratio was significantly higher when the low T dry mix process was used (samples 1-a, 1-b, 1-c and 1-j), compared to when the dry mix high T process (samples 1-d, 1-e, 1-f, 1-g, 1-h, and 1-i) was used to make up the elastomer composite masterbatch. Also, so delta (60 ° C) of the resulting elastomer compound was lower (lower is better) for elastomer compounds using the low T process dry mix compared to elastomer compounds using the dry process mix of T high. Carbon black dispersion was acceptable in all samples (ie, less than 10% of the undispersed area of carbon black particles of at least 10 microns in a larger dimension).
[0128] Table 4
[0130]
[0131]
[0133] Example 2
[0134] This example was performed to illustrate the benefits of the low T process for composing the elastomer composite masterbatch with the same, or with different, elastomer additive.
[0135] The elastomer composite masterbatch ("MB") was made according to EXAMPLES Materials and Methods, as described above, except that PROPEL® E7 carbon black obtained from Cabot Corporation, Boston, MA, was used. in the MB. In samples of MB mixed with butadiene rubber as elastomeric additive, BUNA® CB22 butadiene rubber, obtained from Lanxess, Cologne, Germany was used. In samples of MB mixed with natural rubber as an elastomer additive, SMR20 natural rubber, obtained from Lee Rubber, Kuala Lumpur, Malaysia was used.
[0136] Mix and cure
[0137] All the MB samples were composed by the low T process, according to the formulation in Table 1 and the procedure described in Table 2 ("Stage 2") Low T process. The amounts of MB and the second additive of unfilled elastomer (either natural rubber "NR" or butadiene rubber "BR") were selected in such a way that the final compound comprised a dilute amount of carbon black (41, 44 or 50 phr of CB) relative to the initial MB (55 phr of carbon black) as set out in Table 5.
[0138] The properties of the compound were measured by the methods described in the previous examples. The Montech VMV3000 equipment (MonTech USA LLC, Columbia City, IN), adjusted to the Mooney ML profile (1 4) @ 100C (large rotor, 1 minute preheat, 4 minute test) was used to measure Mooney values.
[0139] Results
[0140] As shown in Table 5, hysteresis and mechanical strengthening properties were favorable for compounds comprising MB made with 50 phr of PROPEL® E7 carbon black and NR elastomer additives. Carbon black dispersion was acceptable in all samples (ie, less than 10 % of the undispersed area of carbon black particles of at least 10 microns in a larger dimension). Tan delta decreased to 44 and 41 phr of CB, while the mechanical reinforcement properties, M300 and M300 / M100, unexpectedly improved in the 44 and 41 phr carbon black samples, relative to the carbon black samples of 50 phr. Furthermore, the low T stage one process used to disperse the elastomer additive in the MB was carried out for a short period of mixing time with low energy consumption relative to several of the high T processes carried out. performed in Example 1. In one of the high T process samples from Example 1, sample 1-f, step one was run for 180 seconds with an energy input of 0.35 kWhr, but the properties of the hysteresis compound and the M300 / M100 mechanical reinforcement produced were inferior to comparable low-T process samples described in Table 5 made with a mix time of Stage one of 180 seconds and less energy (0.27 to 0.30 kWhr). Even the inventive samples of Example 2 were observed to have lower carbon black contents (44 and 41 phr).
[0141] The Mooney viscosity values (ML 1 + 4 @ 100 ° C) measured for the samples in Table 5 indicate that the low T process and the mixed elastomer materials made by the process are satisfactory for the use of these compounds in other processing operations to manufacture finished rubber articles.
[0142] Table 5
[0144]
[0145]
[0147] to. NR = natural rubber; BR = butadiene rubber
[0148] b. CB = carbon black PROPEL® E7
[0150] Example 3
[0151] This example was conducted to study the effects of the low-T process versus the high-T process composition for various carbon blacks in the MB, for various elastomer additives, and for a second elastomer composite masterbatch additive ( "MB2"), and to compare the use of MB in the dry mix mix composition with the dry mix composition made without using MB.
[0152] Mix and cure
[0153] The dry mixed compounds not containing MB were prepared according to the formulation of Table 6 and the process described in the dry mix process of Table 7.
[0154] The MB2 masterbatch additives were manufactured according to the formulations in Table 8 and the process described in the Second Masterbatch Process of Table 9. The MB and MB2 masterbatches were combined according to the formulation in Table 10 and the Low T and High T Processes of Table 11 using the BR and NR elastomer additives described in Example 2.
[0155] All other MB samples were combined by the low T process or the high T process, according to the formulation in Table 1 and the processes described in Table 11, using the BR and NR elastomer additives described in Example 2. The compounding process selected for each sample is shown in Table 12. The amounts of MB, the second unfilled elastomer additive and the MB2 additive were selected so that the final compound comprised a dilute amount of carbon black (44 or 50 phr of CB) with respect to the starting MB (containing 50 or 55 phr of carbon black) as stated in Table 10. Carbon blacks used in the MB were N134 ("A"), PROPEL® E7 ("B") or CRX1346 ™ ("C") carbon blacks, obtained from Cabot Corporation, Boston, MA. The properties of the compound were measured by the methods described in the previous examples.
[0156] Table 6 Dry mix
[0160] * N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine
[0161] ** N-tert-butyl-2-benzothiazole sulfonamide
[0163] Table 7 Dry mix process
[0166]
[0167]
[0169] Table 8-ME12 Formulations
[0171] * N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine
[0173] Table 10 Mixing compound MB MB2
[0176] * N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine ** N-cyclohexyl-2-benzothiazole sulfenamide T l 11 m MB MB2 Pr T
[0177]
[0178] Table 11 Compound MB MB2 High T process
[0181] Vulcanization was carried out in a press heated to 150 ° C for a time determined by a conventional rubber rheometer (ie, T90 10% of T90, where T90 is the time to achieve a vulcanization of 90%).
[0182] Table 12
[0183]
[0184]
[0186] to. Carbon Black Sample A = N134, B = Propel® E7 Carbon Black, and C = CRX1346 ™ Carbon Black.
[0187] b. NR = natural rubber; BR = butadiene rubber (80:20, NR: BR)
[0188] c. See Tables 8 and 9 for MB2 masterbatch additive: NR / BR 90/10 elastomer is mixed with 50 phr carbon black (A) or (B).
[0190] Results
[0191] The data in Table 12 demonstrate that relative to the high T with MB process or a conventional dry mix process without MB, the low T process produced better M300 and M300 / M100 reinforcing properties, and, with one exception for carbon black B, enhanced tan delta in compounds made with pure MB, or MB mixed with an elastomer additive, or MB mixed with a masterbatch additive MB2, in formulations containing various carbon black reinforcing fillers and elastomer additives. Such benefits of the low T process were seen despite the lower temperature, less time, and less energy introduced into the elastomeric materials during Stage one of mixing. Carbon black dispersion was acceptable in all examples (ie, less than 10% undispersed area of carbon black particles of at least 10 microns in a larger dimension). The Mooney viscosity data (i.e., values in the 65 to 95 range for 50 phr fill, aiming at around 70-80 and a preference for the upper end of the range) confirm the low T process and the blended elastomer materials made by the process are satisfactory for use of the compounds in further processing operations for the manufacture of finished rubber articles. Overall, these data demonstrate that the low T process for MB dry mix compounds is a more energy efficient process capable of producing improved and / or equivalent elastomeric compounds relative to those made by less efficient conventional mixing processes.
[0192] Example 4
[0193] This example was performed to study the effects of the low T process versus the composition of the high T process for mixing silica filler additives and elastomers in a MB, specifically the effects of the low T process versus the composition of the process. high T for mixtures of two masterbatches, one is the MB manufactured according to EXAMPLES Materials and Methods, as described above, and the other is a masterbatch MB2 comprising silica.
[0194] Mix and cure
[0195] The MB samples were composed by the low T process or the high T process, according to the formulation in Table 1 and the processes identified in Tables 19-1 and 19-2, below. Samples containing elastomer and pre-bonded silica additives were prepared according to the formulations in Table 13 and combined with MB by the low T process or the high T process in Table 14. MB2 additives containing silica were prepared according to the formulation in Table 15 and the process described in Table 16. Masterbatches MB and MB2 were combined according to the formulation in Table 17 and either the Low T Process or the High T Process from Table 18.
[0196] The elastomer additive was the NR described in Example 2. The silica fill additive was Zeosil® 1165MP silica, obtained from Solvay SA, or Agilon® 400GD pre-bonded (hydrophobic) silica, obtained from PPG Industries, Inc. These additives were used in the final compound in the amounts indicated in Tables 19-1 and 19-2. The amounts of MB, MB2, silica, NR and other additives were selected so that the final compound comprised 50 phr of filler. The carbon black used in the MB was N134 carbon black or Propel® E7 carbon black, obtained from Cabot Corporation, Boston, MA.
[0197] The properties of the compound were measured by the methods described in the previous examples. The breaking values were measured by the ASTM D-624-B method.
[0198] Table 13-Silica Formulations
[0202] * N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine
[0203] ** N- tert-butyl-2-benzothiazole sulfonamide
[0205] T l 14 mil Pr T
[0208]
[0209]
[0211] Table 14 Silica Compound High T Process
[0212]
[0214]
[0216] Table 15-Silica formulation of MB2
[0219] * N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine Table 16 MB2-silica masterbatch process
[0220]
[0221] Table 17 MB2-Silica Compounds
[0224] * N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine ** N-cyclohexyl-2-benzothiazole sulfonamide
[0225] T l 1 Pr T MB2- íli
[0226]
[0227]
[0229] Table 18 High T MB2-Silica process
[0231] T l 1-1
[0232]
[0234]
[0236] to. carbon black N134; elastomer additive NR; Agilon®400GD pre-bonded silica filler additive.
[0237] Table 19 - 2
[0238]
[0240] to. Propel® E7 Carbon Black; elastomer additive NR; Zeosil®1165MP silica, with Si69 coupling agent.
[0241] b. MB2 contained 50 phr of Zeosil®1165MP silica in NR, 5 phr Si69 coupler and 1.5 phr antioxidant (6PPD).
[0242] c. The energy input data was not recorded for the Stage 1 mix, but generally followed the Stage 1 mix time.
[0243] Results
[0244] The data in Table 19-1 demonstrate that the low-T process produces elastomer compounds with a filler additive that have improved hysteresis and mechanical reinforcement properties than the high-T process with a final compound silica content of up to 10 phr of silica. With higher silica content, i.e. 15 phr of silica that is mixed without using an MB2 additive, the benefit of the low T process is less evident and the hysteresis and mechanical reinforcement properties of the elastomer compound produced become equivalent to those produced by the high T.
[0245] The date in Table 19-2 demonstrates that using an MB2 additive in which elastomer and silica are pre-mixed at a temperature of at least 130 degrees C, the low T process to compound MB with such MB2 produced an M300 improved, M300 / M100, and tear mechanical reinforcing properties relative to the high-T process. As noted above, a high-T process sample made with 15 phr silica and NR that had not been mixed in an MB2 (ie, sample 7 (11 -g) had less favorable mechanical reinforcing properties. Therefore, improved silica compounds were made from a mixture of MB and MB2, relative to a comparable equivalent mixture made without MB2, in the process of the invention.
[0246] Carbon black dispersion was acceptable in all samples (ie, less than 10% of the undispersed area of carbon black particles of at least 10 microns in a larger dimension). Mooney's viscosity data confirms that the low T process and the blended elastomer compounds manufactured by the process are satisfactory for use of the compounds in further processing operations for the manufacture of finished rubber articles. Overall, these data demonstrate the low T process for dry mix of MB silica-containing compounds, particularly when an MB2 additive is selected for compounds with higher silica content, it is a more energy efficient process capable of producing compounds. Improved elastomerics and / or equivalents over those made by less efficient conventional mixing processes.
[0247] While this invention has been particularly shown and described with reference to preferred implementations thereof, those skilled in the art will understand that various changes in shape and detail can be made without departing from scope of the invention encompassed by the appended claims.
[0248] Applicant specifically incorporates the entire content of all cited references in this disclosure. Furthermore, when an amount, concentration or other value or parameter is given as a range, preferred range, or a list of upper preferable values and lower preferable values, this should be understood as specifically revealing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the ranges are disclosed separately. Where a range of numerical values is mentioned in this document, unless otherwise indicated, the range is intended to include the end points of the range, and all integers and fractions within the range. The scope of the invention is not intended to be limited to the specific values mentioned when defining a range.
[0249] Other embodiments of the present invention will be apparent to those skilled in the art from a consideration of the present specification and practice of the present invention described herein. The present specification and examples are intended to be construed as examples only with the true scope and spirit of the invention as indicated by the following claims and equivalents thereof.

权利要求:
Claims (43)
[1]
1 A method for producing an elastomer composite, comprising: preparing an elastomer composite masterbatch from an elastomer containing fluid and particulate filler suspension; Y
dry mixing in a multi-stage mixing process, said elastomer composite material masterbatch with at least one additive at a process temperature to obtain an elastomer composite, wherein
a) the process temperature in stage one of a two-stage mixing process is below 130 degrees C in stage one and does not exceed 120 degrees C in stage two of the two-stage mixing process when a healing agent in stage two of the two-stage mix, and
b) the process temperature is below 130 degrees C in stage one of a multi-stage mixing process and is below 130 degrees C in later stages of the multi-stage mixing process when there is no curing agent in the later stages of the multi-stage mixing process; Y
c) the process temperature is below 130 degrees C in stage one of a multi-stage mixing process and is below 120 degrees C in the later stages of the multi-stage mixing process when a curative agent is present in the later stages of the multi-stage mixing process.
wherein in said step one for any of a), b) or c), an energy applied during said dry mixing is reduced by at least 10-50% and a mixing time is reduced by at least 10-60% while achieve at least equivalent mechanical and dynamic properties in the elastomer compound compared to the same process but mixing in step one at a temperature of at least 130 degrees C, and wherein said elastomer compound after said two-stage mixing or Multi-stage mixing has a Mooney viscosity value of about 65 to 90 ° C.
[2]
2. The method of claim 1, wherein, prior to said dry mixing, the method further comprises:
a) drying the elastomer composite masterbatch;
b) chewing the elastomer composite masterbatch to obtain a dry, mechanically worked elastomer composite in strip form;
c) packaging the machined dry elastomer composite material strips to obtain a packaged product; Y
d)
[3]
3.
[4]
Four.
[5]
5.
[6]
6.
[7]
7. - The method of claim 1, wherein the at least one additive comprises at least one additional elastomer.
[8]
8.
[9]
9.
[10]
10.
[11]
eleven.
[12]
12. - The method of claim 1, wherein the at least one additive comprises a second elastomer masterbatch of at least one additional elastomer and a particulate filler.
[13]
13.
[14]
14.
[15]
fifteen.
[16]
16. - The method of claim 12, wherein the second elastomer composite material masterbatch comprises silica filler and at least one elastomer selected from natural rubber and butadiene rubber and combinations thereof.
[17]
17.
[18]
18.
[19]
19.
[20]
twenty.
[21]
twenty-one.
[22]
22.
[23]
2. 3.
[24]
24. - The method of claim 23, wherein the drying, mixing and drying of the additive are carried out continuously.
[25]
25.
[26]
26. - The method of claim 1, wherein the dry mix is carried out in a rubber composition equipment selected from internal mixers, extruders, mixers equipped with interleaved rotors, mixers equipped with tangential rotors, closed mixers, open mixers, laminators and their combinations.
[27]
27.
[28]
28. - The method of claim 1, wherein the at least one additive is added as one or more premixed mixture (s) of two or more additives.
[29]
29. - The method of claim 1, wherein the at least one additive is added in a second elastomer masterbatch.
[30]
30.
[31]
31. - The method of claim 30, wherein the particulate filler suspension comprises water and a filler selected from carbon black, silica, silica-treated carbon black, silica-coated carbon black, or any combination thereof.
[32]
32.
[33]
33. - A method for improving the mechanical reinforcing properties in a filler-reinforced rubber compound comprising using the method of any preceding claim to form the filler-reinforced rubber compound.
[34]
3. 4.
[35]
35. - An article comprising the elastomer compound of claim 32.
[36]
36.
[37]
37.
[38]
38. - The method of claim 1, wherein said process temperature when said curative is not present is 90 to 129 degrees C and when said curative is present, it is 90 to 119 degrees C.
[39]
39.
[40]
40. - The method of claim 1, wherein said additive comprises at least one elastomer masterbatch additive, and wherein the elastomer compound has a filler of 20 phr to 75 phr and wherein a weight ratio of elastomers between said elastomeric composite masterbatch and said elastomeric masterbatch additive is from 50:50 to 5:95.
[41]
41.
[42]
42. - A method for producing an elastomer composite, comprising: preparing an elastomer composite masterbatch from an elastomer containing fluid and particulate filler suspension; Y
dry mixing in a one-stage mixing process, said elastomer composite material masterbatch with at least one additive at a process temperature to obtain an elastomer composite, wherein
a) the process temperature in a one-stage mixing process is below 130 degrees C when no curative is present, and below 120 degrees C when a curative is present, and
wherein the energy applied during said dry mix is reduced by at least 10
50% and optionally the mixing time is reduced by at least 10-60%, while
at least equivalent mechanical and dynamic properties are achieved in the compound
of elastomer compared to the same process but dry mixing at a temperature of at least 130 degrees C before the addition of curatives, and where
said elastomer compound after said mixing has a viscosity value
of Mooney from about 65 to 90.
[43]
43. The method of claim 42, wherein said one-step mixing process is at a temperature of 90 to 129 ° C when a curative is no longer present.
a temperature of 90 to 119 ° C when a curative is present.

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优先权:

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申请号 | 申请日 | 专利标题

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US201762584588P| true| 2017-11-10|2017-11-10|

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PCT/US2018/059762|WO2019094551A1|2017-11-10|2018-11-08|Methods of producing an elastomer compound and elastomer compounds|

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