 production method of a coagulated latex composite, an elastomer composite formed by said method and
专利摘要:
formation of coagulated latex composite. a method of producing a coagulated latex composite. a coagulation mixture of a first elastomer latex and a particulate filler slurry is flowed through a conduit, and a second elastomer latex is introduced into the coagulation mixture stream. 公开号:BR112012008314B1 申请号:R112012008314 申请日:2010-09-16 公开日:2020-02-04 发明作者:Das Thiruhelvanathan Anthony；Mariadass Bernard；Kwang Lee Boon；Wang Meng-Jiao；Karasu Govindan Thirunavuc；Wang Ting；Zhang Xuan 申请人:Cabot Corp； IPC主号:
专利说明:
METHOD OF PRODUCTION OF A COAGULATED LATEX COMPOSITE, ELASTOMER COMPOSITE FORMED BY THE METHOD AND APPROPRIATE APPARATUS TO PERFORM THE METHOD BACKGROUND OF THE INVENTION 1. Field of the Invention. This invention relates to the introduction of additional elastomer latex into a latex clot composite. 2. Description of Related Art. Numerous products of commercial significance are formed of elastomeric compositions in which the particulate filler is dispersed in any of several synthetic elastomers, natural rubber or mixtures of elastomers. Carbon black, for example, is widely used as a reinforcing agent for natural rubber and other elastomers. It is common to produce a masterbatch, that is, a filler elastomer premix, and several optional additives, such as dilution oil. The carbon black masterbatch is prepared with different grades of commercially available carbon black, which vary both in surface area per unit weight and in structure, which describes the size and complexity of carbon black aggregates formed by particle fusion carbon black primaries to each other. Numerous products of commercial significance are formed from such elastomeric compositions of carbon black particulate filling dispersed in natural rubber. Such products include, for example, vehicle tires, in which different elastomeric compositions can be used for the stirrup portion, the side walls, wire film and the housing. Other products include, for example, Petition 870190100968, of 10/08/2019, p. 8/69 2/62 motor for mounting bushings, conveyor belts, windshield wipers and the like. There are a variety of methods for producing carbon black masterbatches. In one method, described in U.S. Patent No. 6,841,606 (the '606 patent), a carbon black suspension and an elastomer latex are combined in a vat and then coagulated by the addition of a coagulant, such as an acid . In a variation of this process, described in Japanese Patent Publication No. 2005220187, natural rubber latex is diluted to 20% of the rubber content (about 24% rubber) and combined with a protease to cleave amide bonds from non-components latex rubber. Cleavage is believed to improve the performance of the final rubber product. In another method, described in U.S. Patent No. 6,048,923, the contents of which are hereby incorporated by reference, a continuous flow of a first fluid, including an elastomer latex, is fed to the mixing zone of a clot reactor. A continuous flow of a second fluid including a carbon black suspension is fed under pressure to the mixing zone to form a mixture with the elastomer latex. The mixture of the two fluids is energetic enough to substantially completely coagulate the elastomer latex with the carbon black, before a discharge end of the clot reactor. As disclosed in U.S. Patent No. 6,075,084, the additional elastomer can be added to the material from which it emerges from the discharge end of the clot reactor. As disclosed in U.S. Patent No. 6,929,783, the clot can then be fed to a Petition 870190100968, of 10/08/2019, p. 9/69 3/62 dehydration extruder. At high carbon black charges, the clot emerges from the clot reactor not as a continuous stream of carbon black elastomer composite, but as a plurality of discrete regions of carbon black elastomer composites carried by a substantially aqueous phase free of clotting. Generally, such discontinuous material does not pass as easily through the dehydration extruder and can flow back into the dehydration extruder, causing clogging. Therefore, it is desirable to prepare a continuous flow of clot containing a high volume fraction of carbon black that can be more easily manipulated in an apparatus such as a dewatering extruder. SUMMARY OF THE INVENTION In one embodiment, the invention is a method of producing a coagulated latex composite. The method includes flowing a coagulation mixture of a first elastomer latex comprising a first elastomer and a particulate filler suspension along a conduit, and introducing a second elastomer latex comprising a second elastomer into the flow of the coagulation mixture. The method may also include, before flowing the coagulation mixture, generating the coagulation mixture by feeding a continuous flow of the first elastomer latex to a mixing zone of a clot reactor defining an elongated clot zone extending from the mixing zone at a discharge end and comprises the duct, and feeding a continuous flow of a fluid comprising particulate pressure under pressure into the mixing zone Petition 870190100968, of 10/08/2019, p. 10/69 4/62 of the clot reactor to form the clotting mixture. The continuous flow of the fluid comprising particulate filling can have a speed of about 30 m / s to about 250 m / s, the continuous flow of the first elastomer latex can have a speed of, at most, about 10 m / s , and, under these conditions, a residence time of the coagulation mixture in the clot reactor before introducing the second elastomer latex can be from 1 x 10 -2 s to about 6 x 10 -2 s. The conduit may include a first conduit portion having a first diameter, a second conduit portion having a second diameter larger than the first diameter, and a transition zone therebetween that has a diameter that increases from the first diameter for the second diameter, and the flow may include flowing the coagulant mixture into the second conduit portion from the first conduit portion, and the introduction may include The introduction of the second latex in elastomer at mixture in coagulation in the region of transition. Flow the mixture coagulant can include flow The mixture in coagulation by region in transition, in turbulent flow conditions. The amount of the second elastomer in the composite can be from about 0.5% by weight to about 50% by weight, for example, from about 16% by weight to about 38% by weight. The second elastomer can be a synthetic elastomer or natural rubber latex. Natural rubber latex can include field latex, latex concentrate, latex film, or a combination of two or more of these. A component of natural rubber latex may have been chemically modified or Petition 870190100968, of 10/08/2019, p. 11/69 5/62 enzymatically. The particulate filler may include a carbon black with a surface area of at least 95 m 2 / g, as measured by the STSA and an adsorption of dibutyl phthalate of at least 80 ml / 100g, and the coagulated latex composite may include at least 65 phr of such a carbon black. The particulate filler may include a carbon black with a surface area of at least 68 m 2 / g, measured by the STSA, for example, at least 75 m 2 / g, and an adsorption of dibutyl phthalate of at least 60 ml / 100g, and the coagulated latex composite can include at least 70 phr of such carbon black. The particulate filler can include a carbon black with a dibutyl phthalate adsorption of at least 60 ml / 100g, and the carbon black can have a surface area and be present in the coagulated latex composite in an amount that satisfies L> - 0.26 * S + 94, where L is the amount of carbon black in the latex composite coagulated in parts per hundred of rubber (phr) and S is the surface area in m 2 / g, measured by STSA. In another embodiment, the invention is an elastomer composite formed by the method of flowing a coagulation mixture of a first elastomer latex and a particulate filling suspension along a conduit, and introducing a second elastomer latex to the mixture flow coagulation. The method may also include, before the coagulation mixture flows, the generation of the coagulation mixture by feeding a continuous flow of the first elastomer latex to a mixing zone of a clot reactor. Petition 870190100968, of 10/08/2019, p. 12/69 6/62 defining an elongated clot zone extending from the mixing zone to a discharge end comprising the duct, and feeding a continuous flow of a fluid comprising particulate pressure under pressure into the mixing zone of the reactor. clot to form the coagulation mixture. The continuous flow of the fluid comprising particulate filling can have a speed of about 30 m / s to about 250 m / s, the continuous flow of the first elastomer latex can have a speed of, at most, about 10 m / s , and, under these conditions, a residence time of the coagulation mixture in the clot reactor before the introduction of the second elastomer latex can be from 1x 10 -2 s to about 6x10 -2 s. The conduit may include a first conduit portion having a first diameter, a second conduit portion having a second diameter larger than the first diameter, and a transition zone therebetween that has a diameter that increases from the first diameter for the second diameter, where the flow may include flowing the coagulant mixture into the second conduit portion from the first conduit portion, and the introduction may include introducing the second elastomer latex into the coagulation mixture in the transition region . The flow of the coagulant mixture may include flowing the coagulation mixture through the transition region, under turbulent flow conditions. The amount of the second elastomer in the composite is from about 0.5% by weight to about 50% by weight, for example, from about 16% by weight to about 38% by weight. The second Petition 870190100968, of 10/08/2019, p. 13/69 7/62 elastomer can be a synthetic elastomer or natural rubber latex. Natural rubber latex can include field latex, latex concentrate, latex film, or a combination of two or more of these. A component of natural rubber latex may have been modified chemically or enzymatically. The particulate filler can include a carbon black with a surface area of at least 95 m 2 / g, measured by STSA and an adsorption of dibutyl phthalate of at least 80 ml / 100g, and the elastomer composite can include at least 65 phr of such a carbon black. The particulate filler may include a carbon black with a surface area of at least 68 m 2 / g, measured by the STSA, for example, at least 75 m 2 / g, and an adsorption of dibutyl phthalate of at least 60 ml / 100g, and wherein the elastomer composite can include at least 70 phr of such a carbon black. The particulate filler can include a carbon black with a dibutyl phthalate adsorption of at least 60 ml / 100g, and a carbon black, can have a surface area and be present in the elastomer composite in an amount that satisfies L> 0, 26 * S + 94, where L is the amount of carbon black in the elastomer composite in parts per hundred of rubber (phr) and S is the surface area in m 2 / g, measured by STSA. In another embodiment, the invention is a method for producing a coagulated latex composite. The method includes generating a flow of a coagulation mixture of an elastomer latex comprising a first elastomer and a particulate filler suspension having a first degree of turbulence, causing the first degree of Petition 870190100968, of 10/08/2019, p. 14/69 8/62 turbulence change to a second degree of turbulence, and introducing a second elastomer latex to the clot at a location where the clot flow has the second degree of turbulence. The generation of a flow may include feeding a continuous flow of the first elastomer latex to a mixing zone of a clot reactor defining an elongated clot zone that extends from the mixing zone to a discharge end and a continuous flow feeding the particulate filling suspension under pressure to the mixing zone of the clot reactor to form the coagulation mixture. The continuous flow of the fluid comprising particulate filling can have a speed of about 30 m / s to about 250 m / s, the continuous flow of the first elastomer latex can have a speed of, at most, about 10 m / s, and, under these conditions, a residence time of the coagulation mixture in the clot reactor before the introduction of the second elastomer latex can be from 1 x 10 -2 s to about 6 x 10 -2 s. The amount of the second elastomer in the composite can be from about 0.5% by weight to about 50% by weight, for example, from about 16% by weight to about 38% by weight. The second elastomer can be a synthetic elastomer or natural rubber latex. Natural rubber latex can include field latex, latex concentrate, latex film, or a combination of two or more of these. A component of natural rubber latex may have been modified chemically or enzymatically. The particulate filler may include a carbon black with a surface area of at least 95 m 2 / g, Petition 870190100968, of 10/08/2019, p. 15/69 9/62 measured by STSA and a dibutyl phthalate adsorption of at least 80 ml / 100g, and the coagulated latex composite can include at least 65 phr of a carbon black. The particulate filler may include a carbon black with a surface area of at least 68 m 2 / g, measured by the STSA, for example, at least 75 m 2 / g, and an adsorption of dibutyl phthalate of at least 60 ml / 100g, and the coagulated latex composite can include at least 70 phr of such carbon black. The particulate filler can include a carbon black with a dibutyl phthalate adsorption of at least 60 ml / 100g, and such a carbon black can have a surface area and be present in the coagulated latex composite in an amount that satisfies L> -0.26 * S + 94, where L is the amount of carbon black in the latex composite coagulated in parts per hundred of rubber (phr) and S is the surface area in m 2 / g, measured by STSA. In another embodiment, the invention is an apparatus comprising a clot reactor that has a mixing portion and a generally tubular diffusing portion extending with the progressive increase in cross-sectional area from an inlet end to a discharge end open. The apparatus is further characterized by a supply tube terminating in an injection port adapted and constructed so as to provide a fluid for the diffuser portion in a portal arranged between the inlet end and the open discharge end. The diffuser portion may include a first diffuser section having a first diameter, a second diffuser section having a second diameter, the second diameter Petition 870190100968, of 10/08/2019, p. 16/69 10/62 being larger than the first diameter, and a transition region between said first and second sections and having a diameter that increases from the first diameter to the second diameter, in which the portal is arranged in the transition region. The apparatus may further include at least one additional diffuser section disposed downstream of the second diffuser section and having a larger diameter than the second diameter. The apparatus may further include at least one additional diffuser section disposed between the mixing portion and the first diffuser portion and having a smaller diameter than the first diameter. It should be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide a further explanation of the present invention, as claimed. BRIEF DESCRIPTION OF THE DRAWING The invention is described with reference to the various figures in the drawing, in which: Figure 1 is a schematic diagram of an apparatus for producing latex clot composite according to an exemplary embodiment of the invention. Figure 2 is a schematic diagram of an apparatus for injecting a second elastomer latex into a clot according to an exemplary embodiment of the invention. Figure 3 is a graph comparing the largest load of carbon blacks obtained during the production of elastomer composites with secondary latex according to an exemplary embodiment of the invention (squares) and without latex Petition 870190100968, of 10/08/2019, p. 17/69 11/62 secondary (diamonds) as a function of the surface area (STSA). Figure 4 is a graph showing the ratio of the maximum N234 carbon black load achieved with respect to the residence time for the production of elastomer composites according to various modalities of the invention (square - production rate from 450500 kg / h (dry base); diamond - production rate of about 200-275 kg / h (dry base, based on primary latex and carbon black only)). DETAILED DESCRIPTION OF THE INVENTION Although it is often desirable to produce elastomer composite with higher filler fillers, such as carbon black in a continuous wet masterbatch process, coagulated rubbers containing higher filler loads are sometimes difficult to pass through processing equipment. downstream. It was unexpectedly discovered that the addition of additional elastomer latex to a coagulation mixture having a high weight fraction of the filling results in the formation of a continuous masterbatch kernel, designated as a coherent clot. Because the coherent clot is a cohesive mass, it does not disintegrate when handled and can be easily dehydrated using standard equipment such as the dehydration extruder available from the French Oil Machinery Company (Piqua, OH, USA). This allows for the continuous production of elastomer composites with high filler loads which can be used to produce vulcanized rubbers having superior properties. In contrast, masterbatch core Petition 870190100968, of 10/08/2019, p. 18/69 12/62 that is not cohesive can flow back into the downstream equipment, causing it to coagulate or become ineffective in dehydration. In one embodiment, a method of producing a coagulated latex composite includes flowing a coagulation mixture of a first elastomer latex and a particulate filler suspension through a conduit and introducing a second elastomer latex into the flow of the mixture of coagulation. As shown in Figure 1, a particulate filler suspension is introduced into a mixing portion 10 of a clot reactor 11 through a filling supply line 12. An elastomer latex is fed into the mixing portion 10 through the supply line. of latex 14. The latex begins to clot in the mixing portion 10, and the coagulant mixture, including elastomer and particulate filler, continues through a diffusing portion 16 of the clot reactor 11. As shown in Figure 1, the diffusing portion 16 has a series of sections 18a-18d, each with a progressively larger diameter than the previous section 18. Preferably, the transition regions 20a-c provide a gradual increase in diameter from one section 18 to the next. One of skill in the art will recognize that the diffusing portion may have sections 18 larger or smaller than those shown in the figure. The second elastomer latex is introduced through the injection system 22. The injection system 22 includes a holding tank 24 and a pump 26 that directs the second elastomer latex into the clot reactor 11 through an injection line. Petition 870190100968, of 10/08/2019, p. 19/69 13/62 28. Preferably, pump 26 is operated to generate sufficient pressure to prevent the flow of the coagulation mixture back into the injection line 28. Another suitable apparatus, for example, pumping of a different type or compression equipment, can be employed to introduce the second elastomer latex into the coagulation mixture. As shown in Figure 1, the second elastomer latex is injected into the coagulation mixture in the transition region 20a. One of skill in the art will recognize that the optimal injection site for the second elastomer latex may vary depending on the composition of the coagulant mixture and the second elastomer latex. Elastomer latex is an emulsion of rubber particles in water. The rubber in the particles is a highly viscous fluid of rubber molecules, surrounded by a covering of naturally occurring substances that stabilize the rubber particles against aggregation and coalescence. The destabilization of the latex causes it to coagulate, that is, the aggregation of rubber particles and coalescence with each other. In preferred embodiments, the speed of the particulate filler suspension is significantly higher than that of the first elastomer latex. The resulting high shear destabilizes the latex. Without being bound by any particular theory, it is believed that the rapid mixing of the particle suspension with the latex results in the decoration of the surface of the rubber particles by the particles, which also destabilizes the latex. Filler particles colliding with each other also form agglomerates that can collide with and destabilize the latex particles. THE Petition 870190100968, of 10/08/2019, p. 20/69 14/62 combination of these factors causes the elastomer latex to destabilize; rubber particles aggregate through the formation of the rubber-rubber contact or by bridging through filler particles on their surfaces, to form aggregates of rubber-fill composites. Without being bound by any particular theory, it is believed that, in the presence of excess particulate filler, the rubber particles or small aggregates of rubber particles become completely decorated with the filler material, with little or no surface area. rubber-free to form rubber-rubber contacts with other rubber particles. This limits the extent to which the aggregates of rubber-fill composites can still aggregate to form a continuous network. Instead, instead of forming a coherent clot, the masterbatch kernel takes the form of discontinuous composite domains dispersed in an aqueous phase. The second elastomer latex introduces fresh latex particles which, since it is not yet decorated with filler particles, can join the aggregates of discrete rubber-fill composites to form a continuous rubber particle composite in the form of a coherent clot . For a device similar to that shown in Figure 1, the factors that influence the coherence of the clot include the amount of particulate filling injected into the mixing block (for example, the target filling charge), the filling morphology (for example, the surface, structure), the residence time of the mixture of the first Petition 870190100968, of 10/08/2019, p. 21/69 15/62 latex elastomer and the suspension filling in particles before introduction of second latex in elastomer, and the proper mix of second latex in elastomer in the mix. According to the theory above, there is a limit beyond which the introduction of additional latex will not allow aggregates of discrete rubber-fill composites to form a coherent clot. That is, if there is excess filling in the mixture after the rubber particles have been completely decorated, the rubber particles in the second elastomer latex stream will become decorated with the excess filling material, instead of binding to the rubber-fill aggregates existing together. Thus, while the use of the second elastomer latex stream can increase the level of filler charge obtained while still producing coherent clot, the potential increase is not infinite. The concentration of the filler in the suspension, the feed rate and the speed of the filler suspension in the mixing zone, and the proportion of the rubber introduced with second elastomer latex with respect to the total rubber in the final composition can all be optimized to maximize the effectiveness of the second elastomer latex. In certain embodiments, the secondary latex improves the achievable filler load (for example, elastomer composite produced with this amount of filler has the morphology of a coherent clot), at least 0.5 phr with respect to the elastomer composite produced in a continuous wet masterbatch process without Petition 870190100968, of 10/08/2019, p. 22/69 16/62 secondary latex, for example, from 0.5 phr to about 15 phr, from about 1 phr to about 14 phr, from about 2 phr to about 13 phr, from about 3 phr to about 12 phr, from about 4 phr to about 11 phr, from about 5 phr to about 10 phr, from about 6 phr to about 9 phr, from about 7 phr to about 8 phr, from about 1 phr to about 7 phr, about 1 phr to about 6 phr, or about 1 phr to about 5 phr. In certain preferred embodiments, the use of secondary latex allows the use of a continuous wet masterbatch process to produce an elastomer composite having at least 65 phr, for example at least 70 phr or 65-75 phr, from a carbon black with a surface area of at least 95 m 2 / g, as measured by the statistical thickness method (STSA), expressed as square meters per gram of carbon black, according to the procedure indicated in ASTM D6556 (STSA) and a structure, measured by dibutyl phthalate (DBP) adsorption (ASTM D6854), of at least 80 ml / 100g, for example, from 80ml / 100g to 160 ml / 100g. Alternatively or in addition, the use of secondary latex may allow the use of a continuous process to produce an elastomer composite having at least 70 phr, for example at least 75 phr or from 70 phr to 80 phr, carbon black with a surface area of at least 68 m 2 / g, measured by the STSA, for example, at least 75 m 2 / g, and a structure, as measured by DBP adsorption, at least 60 ml / 100 g, for example , from 60 ml / 100g to 160 ml / 100g. Alternatively or in addition, the use of secondary latex allows the use of a continuous wet masterbatch process to produce Petition 870190100968, of 10/08/2019, p. 23/69 17/62 elastomer composite containing carbon black having DBP adsorption of at least 60 ml / 100mg, for example at least 80 ml / 100mg, at least 100 ml / 100mg or from 60 ml / 100mg to 160 ml / 100mg, and having a surface area and being present in an amount that satisfies L> -0.26 * S + 94, for example, L> -0.26 * S + 97, or L> -0.26 * S + 100, or L> -0.26 * S + 104, or -0.26 * S + 94 <L <-0.26 * S + 110, where L is the amount of carbon black in the elastomer composite in parts per hundred of rubber (phr) and S is the surface area in m 2 / g measured as STSA (ASTM D6556), where S is optionally at least 65 m 2 / g, at least 95 m 2 / g, at least minus 110 m 2 / g, or 65 m 2 / g to 400 m 2 / g, for example, 65 m 2 / g to 220 m 2 / g, 95 m 2 / g to 200 m 2 / g, or 110 m 2 / g to 180 m 2 / g. In addition, according to the theory above, the effectiveness of the second elastomer latex will be maximized if it is not introduced until substantially all of the filler material has been adsorbed on the rubber particles in the first elastomer latex. Otherwise, the secondary latex particles become decorated with the filler material, instead of bonding to the existing rubber-filler aggregates. The time required for the filler suspension and elastomer latex to mix and allow the filler particles to adsorb on the rubber particles depends, in part, on how energetically the two fluids are mixed together. For apparatus similar to that illustrated in Figure 1, when the first elastomer latex is fed into the mixing portion 10 at a speed of less than about 10 m / s, for example, from about 1 to Petition 870190100968, of 10/08/2019, p. 24/69 18/62 about 10 m / s, about 1.5 to about 8 m / s, about 2 to about 6 m / s, about 3 to about 5 m / s, or about from 4 m / s to about 7 m / s, and the particulate filler suspension is fed into the mixing portion 10 at a speed of at least 30 m / s, for example, about 30 to about 250 m / s or about from 60 to about 150 m / s, a preferred residence time before the injection of the secondary latex, that is, the time required for mixing the particle suspension to travel from the mixing portion 10 to the location where the secondary latex is injected, is about 1 x 10 -2 s to about 6 x 10 -2 s, for example, from 1.5 x 10 -2 s to about 5.5 x 10 -2 s, from about 1, 85 x 10 -2 s to about 5 x 10 -2 s, from about 2 x 10 -2 s to about 4 x 10 -2 s, from about 2.25 x 10 -2 s to about 3 , 5 x 10 -2 s, from about 2.1 x 10 -2 s to about 3 x 10 -2 s, or between about 2.25 x 10 -2 s to about 2.9 x 10 -2 s . We also found that the excessive residence time before the introduction of the second elastomer latex reduces the maximum filling load before the resulting clot is discontinuous, rather than consistent. Without being bound by any particular theory, this can result from incomplete mixing of the second elastomer latex into the coagulation mixture of the first elastomer latex and particle filling suspension, reducing the effectiveness of the secondary latex. We found that if the second elastomer latex is injected too far downstream into the diffuser, it does not mix completely in the flow of the coagulation mixture. The residence time may vary to optimize different operating conditions; suitable intervals may vary Petition 870190100968, of 10/08/2019, p. 25/69 19/62 with the production rate. The physical configuration of the injection system 22 can also be adjusted to optimize the mixture of the second elastomer latex in the mixture. The initial flow of the coagulation mixture through the upstream portions of the diffuser is relatively turbulent. This turbulence gradually decreases as the coagulation mixture proceeds to the bottom, and the flow of the clot from the outlet 34 of the diffuser is approximately laminar. Without being bound by any particular theory, it is believed that the turbulence associated with the expansion of the cross-section flow between the first and second sections 18a and 18b at transition 20a facilitates the mixing of the second elastomer latex injected at that point into the coagulant composite rubber-filler. Other factors influencing mixing and turbulence include the distance from the suspension injection point, the injection speed, the difference in cross-sectional area between the first and second sections of the diffuser, the injection speed of the secondary latex stream, and the injection angle of the secondary latex stream. For example, the second section of diffuser 18b can have a cross-sectional area of about 1.2-3.5 times the cross-sectional area of the first section of diffuser 18a, for example, from about 1.2 to about 1.4 times, about 1.4 to about 1.6 times, about 1.5 to about 1.7 times, about 1.7 to 1.9 times, about 1 , 9 to about 2.1 times, from about 2.1 to about 2.3 times, from about 2.3 to about 2.5 times, from about 2.5 to about 2.7 times , from about 2.7 to about 2.9 times, from about Petition 870190100968, of 10/08/2019, p. 26/69 20/62 from 2.9 to about 3.1 times, from about 3.1 times to about 3.3 times, or from about 3.3 to about 3.5 times greater. In specific examples, the ratio of the cross-sectional areas of sections 18b and 18a can be about 2, about 2.5, or about 3. The lengths of the various sections of the diffuser 18a-18d and the dimensions of sections 18c and 18d downstream can be as described in U.S. Patent No. 6,048,923, the content of which is incorporated herein by reference. In certain embodiments, the length of the first section 18a can be from about 2 inches (5.08 centimeters) to about 9 inches (35.8 cm), for example, from about 2 inches (5.08 centimeters) to about 3 inches (7.62 centimeters), from about 3 inches (7.62 centimeters) to about 4 inches (10.2 cm), about 4 inches (10.2 centimeters) to about 5 inches (12.7 cm), from about 5 inches (12.7 centimeters) to about inches (15.2 cm), from about 6 inches (15.2 centimeters) to about 7 inches (17.8 cm) ), from about inches (17.8 centimeters) to about 8 inches (20.3 cm), or from about 8 inches (20.3 centimeters) to about 9 inches (35.8 centimeters). The optimum length can vary and generally increases with the rate of production. An exemplary approach to introducing the second elastomer latex to the coagulation mixture is illustrated in Figure 2. As shown in Figure 2, the second elastomer latex is introduced into the coagulation mixture through a nozzle 40 that connects the injection line 28 injector 42 having an injection port 42a. An O-ring 44 can be used to improve the seal inside the nozzle 40. While the injector 42 is shown injection the second Petition 870190100968, of 10/08/2019, p. 27/69 21/62 elastomer latex in the coagulant mixture at an angle of 45 degrees to a clot reactor axis, one skilled in the art will recognize that the angle and size of the injector can be varied depending on the composition of the coagulant mixture and the second latex of elastomer. For example, when the injector 42 is at right angles to the wall of the transition area 20a, the angle α of the transition area 20a can be from 0.5 ° to 25 °, for example, 0.5 ° -1 °, 1 ° to 2 °, 2 ° to 3 °, 3 ° to 4 °, 4 ° to 5 °, 5 ° to 6 °, 6 ° to 7 °, 7 ° to 8 °, from 8 ° to 9 °, 9 ° to 10 °, 10 ° to 11 °, 11 ° to 12 °, 12 ° to 13 °, 13 ° to 14 °, 14 ° -15 °, 15 ° 16 °, 16 ° to 17 °, 17 ° to 18 °, 18 ° to 19 °, 19 ° to 20 °, 20 ° to 21 °, 21 ° to 22 °, 22 ° to 23 °, 23 ° to 24 °, or 24 ° to 25 °. In another example, the inside diameter of the injection port 42a can vary from 0.045 to 0.25 inches (0.114 to 0.635 cm), or even larger, depending on the size of the diffuser portion 16. For example, the inside diameter of the injection port 42a can be 0.045 inches (0.11 cm) ) to 0.055 inches (0.14 cm), from 0.055 inches (0.14 cm) to 0.06 inches (0.15 cm), from 0.06 inches (0.15 cm) to 0.065 inches (0.17 cm) cm), from 0.065 inches (0.17 cm) to 0.07 inches (0.18 cm), from 0.07 inches (0.18 cm) to 0.075 inches (0.19 cm), from 0.075 inches (0.19 cm) to 0.08 inches (0.20 centimeters), from 0.08 inches (0.20 cm) to 0.09 inches (0.23 cm), 0.09 inches (0.23 cm) to 0.1 inch (0.25 cm), 0.1 inch (0.25 cm) to 0.125 inch (0.32 cm), from 0.125 inch (0.32 cm) to 0.15 inch (0.38 cm), from 0.15 inches (0.38 cm) to 0.175 inches (0.44 cm), from 0.175 inches (0.44 cm) Petition 870190100968, of 10/08/2019, p. 28/69 22/62 to 0.2 inches (0.51 cm), from 0.2 inches (0.51 cm) to 0.225 inches (0.57 cm), or from 0.225 inches (0.57 cm) to 0.25 inch (0.64 cm). One skilled in the art will recognize that the size of the injection port can be varied depending, for example, on the desired flow rate and pressure. For example, the injection pressure can be 2-8 bar (0.2-0.8 MPa), 3-8 bar (0.3-0.8 MPa), 4-7 bar (0.4-0, 7 MPa), or 5-6 bar (0.5 -0.6 MPa). Other suitable designs can also be employed. For example, the injection port can be gradually reduced inwardly relative to the injector 42 or it can be the same diameter as the injector 42. The second elastomer latex may have the same composition as that used to prepare the coagulation mixture, or it may be different in some way. For example, the second elastomer latex may be an elastomer latex from a different source or with a different concentration of rubber and fluid. Alternatively or in addition, it can undergo different chemical modifications (including no modifications) than the elastomer latex in the first place. In certain embodiments, at least one and, preferably both, the first elastomer latex (i.e., the elastomer latex in the coagulation mixture) and the second elastomer latex are prepared from a natural rubber latex. Examples of natural rubber latex include, but are not limited to, field latex, concentrated latex (produced, for example, by centrifugation, evaporation, or cream formation), latex film (a by-product of the latex centrifugation of Petition 870190100968, of 10/08/2019, p. 29/69 23/62 natural rubber) and mixtures of any two or three of these in any proportion. The latex must be suitable for the selected wet masterbatch process and the intended purpose or application of the final rubber product. Latex is typically supplied in a liquid aqueous vehicle. The selection of a suitable latex or mixture of latexes will be well within the skill of those skilled in the art provided the benefit of the present disclosure and knowledge of the selection criteria, generally well recognized in the industry. Natural rubber latex can also be chemically modified in some way. For example, it can be treated to modify chemically or enzymatically or to reduce various non-rubber components, or the rubber molecules themselves can be modified with various monomers or other chemical groups, such as chlorine. Examples of natural rubber latex chemical modification methods are disclosed in Patent Publications European Nos 1489102, 1816144 and 1834980, Japanese Patent Publications Nos 2006152211, 2006152212, 2006169483, 2006183036, 2006213878, 2006213879, 2007154089 and 2007154095, the US Patents Nos 6841606 and 7312271, and US Patent publication No. 20050148723. Other methods known to those skilled in the art can also be employed. In an alternative embodiment, at least one of the first elastomer latex (i.e., the elastomer latex in the coagulation mixture) and the second elastomer latex is prepared using synthetic elastomer latex. The synthetic elastomer latex elastomer Petition 870190100968, of 10/08/2019, p. 30/69 24/62 can have a glass transition temperature (Tg) as measured by differential scanning calorimetry ranging from about -120 ° C to about 20 ° C. The synthetic latex can be a rubber latex or dienic elastomer. The term "dienic elastomer" or rubber should be understood to mean, in a known manner, one (one or more are understood) elastomer, resulting at least in part (i.e., a homopolymer or a copolymer) of diene monomers (monomers that carry two carbon-carbon double bonds that may or may not be conjugated). These dienic elastomers can be classified into two categories: essentially unsaturated or essentially saturated. The term essentially unsaturated is generally intended for a dienic elastomer resulting in at least part of the conjugated diene monomers having a level of units of diene origin (conjugated dienes), which is greater than 15% (mol%); thus dienic elastomers such as butyl rubber or copolymers of dienes and α olefins of the EPDM type do not come within the previous definition and can in particular be described as essentially saturated dienic elastomers (low or very low level of diene origin units, always less than 15%). In the category of essentially unsaturated dienic elastomers, the term highly unsaturated dienic elastomers is understood to mean in particular, a dienic elastomer having a level of diene origin units (conjugated dienes), which is greater than 50%. The synthetic dienic elastomer of the first elastomer latex or the second elastomer latex according to Petition 870190100968, of 10/08/2019, p. 31/69 The invention is preferably chosen from the group of highly unsaturated dienic elastomers consisting of polybutadienes (abbreviated to BR), synthetic polyisoprene (IR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers. Such copolymers are most preferably chosen from the group consisting of butadiene / styrene copolymers (SBR), isoprene / butadiene copolymers (BIR), isoprene / styrene copolymers (SIR) and isoprene / butadiene / styrene copolymers (SBIR). Elastomers can, for example, be block, random, sequential or micro sequential elastomers and can be prepared in dispersion or in solution, as they can be a coupling and / or branching agent or functionalization with a coupling and / or in starification or functionalizing agent. For coupling with carbon black, mention may be made, for example, of functional groups comprising a C-Sn bond or of amino-functional groups, such as benzophenone, for example, by coupling with an inorganic reinforcement filler, such as silica, for example, silanol functional groups or polysiloxane functional groups having a silanol end (as described, for example, in US 6 013 718), alkoxysilane groups (as described, for example, in US 5,977,238), of carboxyl groups (as described, for example, in US 6,815,473 or in US 2006/0089445) or of polyether groups (as described, for example, in US 6,503,973). It can also be mentioned, other examples of such functionalized elastomers, elastomers (such as SBR, Petition 870190100968, of 10/08/2019, p. 32/69 26/62 BR, NR or IR) of the epoxidated type. The following are preferably suitable: polybutadienes, especially those that have a content of 1.2-units from 4% to 80% or those that have a content of cis-1,4-units greater than 80%, polyisoprene , butadiene / styrene copolymers, in particular those having a styrene content of 5% to 70% by weight, more particularly 10% to 50%, for example, from 20% to 40% by weight, or between about from 23% to about 28% by weight, a content of 1,2-bonds of the butadiene part of 4% to 65% and a content of trans-1,4-bonds of 20% to 80%, butadiene copolymers / isoprene, in particular those that have an isoprene content of 5% to 90% by weight and a glass transition temperature (Tg - measured according to the ASTM standard D 3418-82) from -40 ° C to -80 ° C, copolymers in isoprene or / styrene, in particular those who have one content of styrene 5% a 50% by weight is -25 ° C Tg The -50 ° C. In the case of butadiene / styrene / isoprene copolymers, those having a styrene content of 5% to 50% by weight and more particularly 10% to 40%, an isoprene content of 15% to 60% by weight and more particularly 20% to 50%, a butadiene content of 5% to 50% by weight and more particularly between 20% to 40%, a 1.2-unit content of the butadiene part of 4% to 85%, a content of trans-1,4-units of the butadiene part of 6% to 80%, a content of 1,2- plus 3,4-units of the isoprene part of 5% to 70% and a content of trans-1,4 isoprene part units of 10% to 50%, and more generally any butadiene / styrene / isoprene copolymer having a Tg of -20 ° C to -70 ° C, are particularly suitable. Exemplary synthetic elastomers include, but are not Petition 870190100968, of 10/08/2019, p. 33/69 27/62 are limited to 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl1,3-butadiene, rubbers and polymers (e.g. homopolymers, copolymers and / or terpolymers), where alkyl may be methyl, ethyl, propyl, etc., acrylonitrile, ethylene, and propylene and the like. Examples include, but are not limited to, styrene-butadiene rubber (SBR), polybutadiene, polyisoprene, poly (styrene-co-butadiene), polymers and copolymers of conjugated dienes, such as polybutadiene, polyisoprene, polychloroprene and the like, and copolymers of such dienes conjugated to a copolymerizable monomer containing ethylene therefrom, such as styrene, methyl styrene, chloro-styrene, acrylonitrile, 2-vinyl-pyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2 -vinylpyridine, 2-methyl-5vinylpyridine, allyl-substituted acrylates, vinyl ketone, methyl isopropenyl ketone, methyl vinyl ether, alpha-methyl carboxylic acids and the esters and amides thereof, such as dialkylacrylic acid amide and acrylic acid. Mixtures and / or extended petroleum derivatives of any of the elastomers discussed here can also be used. Copolymers of ethylene and other high alpha-olefins, such as propylene, butene-1 and pentene-1, are also suitable for use in this invention. In some embodiments, it may be desirable to inject a coagulant, for example, an acid or salt solution, together with the elastomer latex stream, to promote elastomer coagulation. The particulate filling fluid can be a fluid suspension of carbon black or any other suitable filling material in a carrier fluid Petition 870190100968, of 10/08/2019, p. 34/69 Appropriate 28/62. The selection of the carrier fluid will largely depend on the choice of particulate filling material and on the system parameters. Both aqueous and non-aqueous liquids can be used, with water being preferred in many modalities, taking into account its availability, cost and suitability for use in the production of carbon black and certain other fill suspensions. Small amounts of water-miscible organic solvents can also be included in aqueous carrier fluids. The selection of the particulate filler material or mixture of particulate fillers depends largely on the intended use of the elastomer masterbatch product. As used herein, particulate filler can include any material that is suitable for use in the masterbatch process used to produce the masterbatch kernel. Suitable particulate fillers include, for example, conductive fillers, reinforcing agents, fillers comprising short fibers (typically having an L / D aspect ratio of less than 40), flakes, etc. In addition to carbon black and silica-type fillers, discussed in more detail below, the fillers can be formed of clay, glass, polymer, such as aramid fiber, etc. It is expected that any filler material suitable for use in elastomer compositions can be incorporated into elastomer compositions according to various embodiments of the invention. Of course, mixtures of the various particulate fillers discussed here can also be used. When a carbon black filling material is Petition 870190100968, of 10/08/2019, p. 35/69 29/62 used, the selection of carbon black will largely depend on the intended use for the elastomer masterbatch product. Optionally, the carbon black filler material can also include any material that can be mixed and combined with a latex in the particular wet masterbatch process selected by the person skilled in the art. Sample particulate fillers include, but are not limited to, carbon black, fumed silica, precipitated silica, coated carbon black, chemically functionalized carbon blacks, such as those with bonded organic groups, and silicon treated carbon black, either alone or in combination with each other. Example carbon blacks include ASTM N100 series - N900 series carbon blacks, for example, N100 series carbon blacks, N200 series carbon blacks, N300 series carbon blacks, N700 series carbon blacks, N800 series carbon, or N900 series carbon blacks. Elastomer composites containing N100, N200, and / or N300 ASTM series blacks and / or carbon blacks having similarly high or higher surface areas, for example, a surface area measured by the statistical thickness method (STSA), expressed as square meters per gram of carbon black, according to the procedure indicated in ASTM D6556 (STSA) of 68 m 2 / g or greater, for example, 75 m 2 / g or greater, or 95 m 2 / g or higher than, for example, 68 m 2 / g to 400 m 2 / g, can especially benefit from the teachings here. In certain preferred embodiments, such carbon blacks have a structure, as measured by dibutyl phthalate adsorption, of at least 60 ml / 100g, for example, Petition 870190100968, of 10/08/2019, p. 36/69 30/62 at least 80 ml / 100g, or from 60 ml / 100g to 160 ml / 100g. Carbon blacks sold under the available brands Regal®, Black Pearls®, Spheron®, Sterling®, and Vulcan® from Cabot Corporation, the Raven®, Statex®, Furnex®, and Neotex® brands and the CD and HV lines available from Colombian Chemicals, and the Corax®, Durax®, Ecorax®, and Purex® brands and the CK line available from Evonik (Degussa) Industries, and other fillers suitable for use in rubber or tire applications, can also be explored for use with various modalities. Suitable chemically functionalized carbon blacks include those described in international application No. PCT / US95 / 16194 (WO 96/18688), the disclosure of which is incorporated herein by reference. Both silicon-coated carbon blacks with silicon-treated can be employed in various modalities. In silicon-treated carbon black, a species containing silicon, such as an oxide or silicon carbide is distributed through at least a portion of the carbon black aggregate as an intrinsic part of the carbon black. Conventional carbon blacks exist in the form of aggregates, with each aggregate consisting of a single phase, which is carbon. This phase can exist in the form of an amorphous carbon and / or graphitic crystallite, and is generally a mixture of the two forms. Carbon black aggregates can be modified by depositing species containing silicon, such as silica, on at least a portion of the surface of the carbon black aggregates. The result can be described as carbon blacks coated with silicon. Petition 870190100968, of 10/08/2019, p. 37/69 31/62 The materials described herein as silicon-treated carbon blacks are not carbon black aggregates that have been coated or otherwise modified, but actually represent a different type of aggregate having two phases. One phase is carbon, which will still be present as graphitic crystallite and / or amorphous carbon, while the second phase is silica (and possibly other species containing silicon). Thus, the silicon-containing species phase of silicon-treated carbon black is an intrinsic part of the aggregate, which is distributed over at least a portion of the aggregate. A variety of blacks treated with silicon is available from Cabot Corporation under the name Ecoblack TM . It will be appreciated that the multiphase aggregates are quite different from the silica coated carbon blacks mentioned above, which consist of single phase carbon black aggregates preformed with silicon containing species deposited on their surface. Such carbon blacks can be treated on the surface in order to place a silica feature on the surface of the carbon black aggregate, as described in, for example, U.S. Patent No. 6,929,783. One or more additives can also be pre-mixed, if appropriate, with the particulate suspension or with the elastomer latex fluid or can be combined with mixing these during coagulation. Additives can also be mixed in the coagulation mixture. Various additives are well known to those of skill in the art and include, for example, antioxidants, antiozonants, plasticizers, processing aids (for example, liquid polymers, oils and Petition 870190100968, of 10/08/2019, p. 38/69 32/62), resins, flame retardants, dilution oils, lubricants, coupling agents, and a mixture of any of them. Exemplary additives include, but are not limited to, zinc oxide and stearic acid. The general use and selection of such additives are well known to those skilled in the art. It should be understood that the elastomer composites disclosed herein include vulcanized (VR), vulcanized thermoplastic (TPV) and thermoplastic elastomers (TPE) and thermoplastic polyolefins (TPO). TPV, TPE, and TPO materials are further classified by their ability to be extruded and molded several times without loss of performance characteristics. The fraction of the second elastomer with respect to the total rubber in the composite (that is, the amount of rubber contributed to the clot per second elastomer latex with respect to the total amount of rubber in the clot) can be adjusted, for example, by adjusting the rates of relative flow of the two elastomer latexes. Other variables that can be manipulated to optimize the filler load include the absolute flow rate of the first elastomer latex and filler suspension (for example, the production rate), the relative flow rate of the first latex elastomer and filler suspension. (for example, the filler load), the location where the second elastomer latex is injected, and the size of the injector 42. The fraction of the second elastomer with respect to the total rubber can be about 0.5% by weight at about 50% by weight, for example from about 1% by weight to about 45% by weight, from about 5% by weight to about 40% by weight, from about 10% Petition 870190100968, of 10/08/2019, p. 39/69 33/62 by weight to about 15% by weight, from about 15% by weight to about 20% by weight, from about 20% by weight to about 25% by weight, from about 25% by weight to about 30% by weight, from about 30% by weight to about 35% by weight, from about 35% by weight to about 40% by weight, or between about 40% by weight and about 45 % by weight. In certain embodiments, the fraction can be from about 16% by weight to about 38% by weight. The proportion of the second elastomer that can be used depends, in part, on the desired composition, but can be physically limited, depending on the amount of the first elastomer latex that must be injected into the mixing portion 10 to generate the initial coagulant mixture. The amount of filling material in the composite in elastomer can to be any quantity in material in filling what is used to make composites in elastomer. For example, rubbers can be produced with at least about 10 phr (parts per hundred of rubber, by weight), at least about 20 phr, at least about 30 phr, at least about 40 phr, at least about 50 phr at least about 55 phr, at least about 60 phr, at least about 65 phr, at least about 70 phr, at least about 75 phr, at least about 80 phr, at least about 85 phr, at least about 90 phr, at least about 95 phr, or at least about 100 phr filler. However, the present teachings will provide greater advantages over other wet masterbatch methods at higher filler loads, for example, from about 40 phr and about 100 phr, from about 50 phr to about 95 phr, in Petition 870190100968, of 10/08/2019, p. 40/69 34/62 fence in 55 phr about 90 phr, about 60 phr a fence in 85 phr, of about 60 phr to about 80 phr, from fence in 65 phr about 75 phr, or about 45 phr a fence in 70 phr. An expert in art will recognize that what constitutes a high load will depend on the morphology of the filler material, including, for example, surface area, and its structure. In some embodiments, the use of secondary latex increases the maximum filler load (for example, the maximum filler load, producing a coherent clot), by about 3% to about 30%, for example, from about 3% to about 5%, from about 5% to about 10%, from about 10% to about 15%, from about 15% to about 20%, from about 20% to about 25 %, or from about 25% to about 30%, with respect to the maximum filler load, while producing a coherent clot, without the use of secondary latex. The masterbatch core produced from the first elastomer latex, the particulate filler suspension, and the second elastomer latex emerge from the discharge end of the clot reactor as a substantially constant flow of clot simultaneously with the ongoing feeding of the latex from elastomer and particulate fill suspension streams in the clot reactor 11. Preferably, the masterbatch core is in the form of a coherent clot, a continuous composite, in which the carbon black is dispersed within the clotted latex, rather than a batch discontinuous flow in which discrete coagulated latex globules are separated by an aqueous carrier. However, the discontinuous clot Petition 870190100968, of 10/08/2019, p. 41/69 35/62 can be processed by batch drying methods, or manual followed by thermal drying. Preferably, the continuous clot is created and then formed into a desirable extrudate, for example, it has about 70-85% water content. After formulation, the resulting masterbatch kernel can be passed on for proper drying and composition of the apparatus. In one embodiment, the masterbatch kernel is passed from the clot reactor 11 to a dewatering extruder by means of a simple gravity drop or other suitable apparatus known to those skilled in the art. The dewatering extruder can bring the elastomer composite of, for example, about 70-85% water, to a desired water content, for example, approximately 1% to 20% water content. The optimum water content may vary with the elastomer used, the type of filling material, and the desired downstream processing procedure. Suitable dewatering extruders are well known and commercially available from, for example, French Oil Mill Machinery Co. (Piqua, Ohio, USA). After dehydration, the resulting dehydrated clot can be dried. In certain embodiments, the dehydrated clot is simply thermally dried. Preferably, the dehydrated clot emerging from the dehydration extruder is mechanically chewed during drying. For example, the dehydrated clot can be mechanically worked with one or more of a continuous mixer, an internal mixer, a twin screw extruder, a single screw extruder, or a mill. Petition 870190100968, of 10/08/2019, p. 42/69 36/62 roll. Suitable killing devices are well known and commercially available including, for example, a Unimix continuous mixer and MVX machine (mixing, aeration, extrusion) from Farrel Corporation of Ansonia, Conn., A long continuous mixer from Pomini, Inc., a Mixer Continuous from Pomini, double rotor co-rotating interleaving extruders, double rotor counter-rotating non-interleaving extruders, Banbury mixers, Brabender mixers, internal interlacing mixers, internal mass mixers, composition extruders continuous, biaxial grinding extruder produced by Kobe Steel, Ltd., and a continuous mixer from Kobe. Alternative grinding apparatus suitable for use with various embodiments of the invention will be familiar to those skilled in the art. Examples of methods for mechanical grinding of dehydrated composite are disclosed in Patents of USA Nos 6,929,783 and 6,841,606, and PCT Order No. US09 / 000732, the contents of all the Which are they on here embedded per reference. In certain modalities, additives can to be combined with the clot dehydrated in the mixer mechanical. Specifically, additives, such as filler material (which can be the same, or different, filler material used in the clot reactor; exemplary fillers include zinc oxide and silica, with zinc oxide also acting as a curing agent) , other elastomers, another masterbatch or additional masterbatch, antioxidants, antiozonants, plasticizers, processing aids (for example, stearic acid, which can Petition 870190100968, of 10/08/2019, p. 43/69 37/62 can also be used as a curing agent, liquid polymers, oils, waxes, and the like), resins, flame retardants, dilution oils, lubricants, and a mixture of any of them, can be added in the mechanical mixer . In certain other embodiments, the additional elastomers can be combined with the dehydrated clot to produce mixtures of elastomers. Exemplary elastomers include, but are not limited to, rubbers, polymers (e.g., homopolymers, copolymers and / or terpolymers) of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dialkyl-1,3-butadiene, where alkyl can be methyl, ethyl, propyl, etc., acrylonitrile, ethylene, and propylene and the like. Mixtures masterbatch production methods are disclosed in our US Patent Nos property 7,105,595, 6,365,663, and 6,075,084. Alternatively or in addition, traditional compositional techniques can be used to combine vulcanizing agents and other additives known in the art with the dehydrated clot or, when a chewing device is used to dry the material, the resulting chewed masterbatch, depending on the intended use . In certain embodiments, the elastomer composite can be used in or produced for use on various parts of a tire, for example, tires, tire tread, tire sidewalls, tire film wires, and cushion gum for retreading tires. Applications other than for additional tires for these elastomer composites include, but are not limited to, engine mount rubber components, grading bands, mining belts, components Petition 870190100968, of 10/08/2019, p. 44/69 38/62 rubber hydro-mounts, bridge bearings, seismic insulators, tracks and track blocks for track propulsion equipment such as excavators, etc., mining equipment such as screens, mining equipment linings, conveyor belts , ramp linings, suspension pump linings, suspension pump components such as thrusters, valve seats, valve bodies, piston shaft, piston rods and pistons, thrusters for various applications, such as mixing suspensions and thrusters suspension pump, milling liners, cyclones and hydrocyclones, and expansion joints, marine equipment such as pump linings (eg, outboard pumps, dredging pumps), hoses (eg, dredging hoses and outboard hoses), and other marine equipment, shaft seal for marine, oil, aerospace and other applications, shaft s propellants, pipe linings to transport, for example, oil sands and / or tar sands, and other applications where abrasion resistance is desired. The present invention will be further clarified through the following examples, which are intended to be exemplary only in nature EXAMPLES EXAMPLE 1 Preparation of carbon black suspensions Dry carbon black (grade indicated in Table 1, below, obtained from Cabot Corporation) was mixed with water and ground to form a suspension with a concentration of about 10-15% by weight. The suspension was Petition 870190100968, of 10/08/2019, p. 45/69 39/62 fed to a homogenizer at an operating pressure of about 3000 psig (20.68 MPa) to produce a finely dispersed carbon black suspension, and the suspension was introduced as a jet into the mixing zone. The flow rate of carbon black was adjusted to around 690960 kg / h (wet basis) to modify the final loading levels of carbon black in composites produced with field latex and up to about 1145 kg / h (base wet) when the latex concentrate was used. Table 1 Carbon Carbon Grade STSA * (m7g) DBP adsorption **(mL / 100g) N234 114 125 N134 131 127 Experimental Negro 1 154 123 * ASTM D6556 * + ASTM D2414 Primary Latex Release Natural rubber latex materials described in Table 2 (field latex, unless otherwise indicated in Table 2) were pumped into the mixing zone of the clot reactor. The latex flow rate was adjusted between about 320-790 kg / h (wet basis) in order to modify the final carbon black loading levels. Carbon black and latex blend The carbon black and latex suspension were mixed by dragging the latex into the carbon black suspension in a mixing portion (for example, mixing portion 10) of a clot reactor similar to that shown in Figure 1. During the process drag, the Petition 870190100968, of 10/08/2019, p. 46/69 40/62 carbon black was intimately mixed in the latex and the coagulated mixture. Secondary latex release Natural rubber latex materials described in Table 2 were pumped at various locations downstream of the mixing portion of the clot reactor at a pressure of 3-8 bar (0.3-0.8MPa) starting at a rate of about 80 kg / hour (wet basis). The latex was injected at a right angle to the wall of the clot reactor to which the injection line (for example, element 28) is attached. The pumping rate was gradually increased to a maximum of 300 kg / h (wet basis) until the clot emerging from the diffuser displays the desired morphology. Downstream of the mixing portion, a diffuser portion had a series of sections, each with a progressively larger diameter than the previous section, with a beveled transition portion between sections. The first section of the diffuser (for example, 18a in Figure 1) was 4 inches (10.2 cm) long, the second section (for example, 18b in Figure 1) was 3 inches (7.6 cm) long. length. The angle of the transition region (for example, α in Figure 2) was 7 degrees. The ratio between the diameters of the second section (for example, 18b in Figure 1) to that of the first section (for example, 18a in Figure 1), was about 1.7. The location where the secondary latex was pumped and the fraction of the rubber of the secondary latex in the final product (ie, the ratio of the rubber of the secondary latex to the total rubber of the primary and secondary latex chains) are shown in Table 2 below . The data shown in bold reflects the maximum load obtained for a given Petition 870190100968, of 10/08/2019, p. 47/69 41/62 secondary latex injection, listed in Table 3 below Table 2 A 3IMM z a erdd)l / ird luiTi-TheThe'β> »Ϊ-ι to Φ With CM O (O dCO O d a rd 2; COCO Φ the Q> 03OCM o <o d<o the CO m CO a cd 2; CM<D U> CQ V * ·ΪΝ dCO d <o « CO cq <Ü .gΕΛ COCM CO 3CNZ a; rdUl / ird δ Iπ]a Έ k — 1 s ÍnCM αCO d CO <D <o CO .gt / j <MCfi to m CM cn CM dCO dCO m CO CO gΪΛ dio O ΪΪCM the CO d CO POO CMT " gw / jΉ φCM d(O the CO CO cM gCfl ^ r σί CO rsj Z gives1 u Φ tf! CM of i 1l / ldJ -> 1 4 g-r CJ p i / i S dj í / j nJ d I Grade CB 1 ’ÜThe_dJF .e73 Έ- l / la & rd ίΐΐ nl 'g' g dJ Λ tf rd ü WP (d bp tfto ert -íThe&dj*rtH o '·· * η * • rd □ • α U Pd P q '··tf cd□^ aU tf P D '··Tf Su PdPΉ□ rM -êU tf Q rd 1/1 Ijj w lb rd 7'.h -ü -fd 'tf a £ ÉN -§ ΰ 2 a | _! Kl djtoa u a>the u <fd '’S djsijed blrd u I frCZN 1 a • · βü'l / l£ * 3 Mrt CM 237 | 307 | 1 1 <8 I the CN □> gí / j CO csí CD O r>CM oh co « 01 COy gí / j «ΪCM <O ΓΟ CD <The CM CM the CO o ΐ - ΐ - COt— gí / j CMCM Φ CM z Oβs• S 2 «JS,atrd 9><0 RCM d CO ΓΜ n 4 .gΪΛ IO<0 O 00 CO CM o <o cM CMThe irt 2 <D 3CMZ The etdCj i / ia -ΰLE gS'l / l Φ The CM CM dIOT * 4Uirt .gtfl W sCMz a rd rt o, U iU O 2 'β £ s í s o u * s CM dit's the4 CMV .gΪΛ ®THE1Λ | GraudeCB £ Jd Ô! Fd _HJ ig 1 o -ü 73 1 u π 5 4J i — 1 i / i l / l O & rd rd rd 'g Έ dj Λ tf rd u tdJ-fd YOUÓL · tfArt -g odJ% 3 £ A JdnU tf n D '··* '*Έ4d□ irM-andÍJ tf n ü '· -ã su Pd P È43□ rS ’êU tf Ω rd 1/1 dj W 1b fd '.h íf -ifl a Γ íi ^ dj O nzi' tí a 2 fl art ã js [_, rt dj § to u 1, rtHi J <fd '’S dJ S fq Urd ω.U Based on carbon black and first latex only * Dry rubber content ** DRC adjusted by dilution with water Petition 870190100968, of 10/08/2019, p. 48/69 42/62 Table 2E Degree of CB I experimental black 1 sCS2 Transition between the first and second sections 1Λ CO (Oj I £ DLO íCOΦ in Hi Hi .1ΪΛ CO N134 |PΓΗ tf tfí M tf <h CM <Λ «S in ôí .§ϊζι s POO <o o n tf σί C * l <O 3 θ CO cs Cfl ΦCO cO00 COHi CS o> cs «0 o> cs £ co cs 303 m<laughs <£> υ Έ1 U The tf o CM w w hi cs i 1 1 303 σ>3 Experimental black 1 1 | edl / l1)edLedhi Ijj h un8huh the o The rt io6io rtOIO Q <O MCN 303 tftf CO Cj<35CM CO oCO COCJ <o CS CS 303 cn ΙΌ s <O CS co ô CO CO o <o CS Hi 303 hey CD the CO CD0QCN CO oCO <o o CO ÍN rs CJ .§03 COThe tf Uüώ Ü o .2 ! S .. £ 0J Ί3 9 4 ^ i / i Έ Ϊ3 Ún • ô & ed ed ed 'g u & Ϊ3 ed 3 U o o '> ed£ Phu* ed a- · * Λ * ^ ed 'tí U tí P Ϊ34uP YOU5u tí QAND-IP edl / l U «A, ed i “li tí í dJ □ * 1 esΰHβ r — I ed li6 teOO1, edThe U 'l l / l ij w fe, u IÜ 5 = 11 ed 'ed ttfj' β u 8 * Based on carbon black and first latex only Petition 870190100968, of 10/08/2019, p. 49/69 43/62 For successful examples that incorporate secondary latex according to one embodiment of the invention, a masterbatch kernel ejected from the clot reactor as a coherent continuous flow of clot. Unsuccessful examples employing secondary latex can be contrasted with suitable samples with similar operating conditions, in general, rubber recovered from such examples contained higher carbon black charges. Such samples emerged from the clot reactor as a clot, discontinuous of sand that caused the dehydration extruder to recede. Table 3 below shows the maximum load, that is, the maximum load content in the elastomer composite, in parts per hundred of rubber (phr), for which the coherent clot was produced (that is, attempts at crumb production) of masterbatch with higher filling material content did not result in a coherent clot). Table 3 Injection point in diffuser Maximum carbon black charge, phr N234 N134 BlackExperimental 1 Control(without injection) 59.7 * 54.9 49.3 Middle of first section 59.9 - - 1 downstream from the middle of the first section 52.5 - - Transition between the first and second sections 71.1 64.4 61.6 1 upstream from the middle of the second section 65 - 51.4 middle of the second section 62.1 - - * irregularly discontinuous clot Petition 870190100968, of 10/08/2019, p. 50/69 44/62 The results show that the operational variables such as the flow rate of the primary and secondary latex streams, the production rate, the proportion of secondary rubber, and the carbon black charge can be optimized in relation to each other to improve the processability and increases the load percentage. Figure 3 shows the highest loads obtained with and without secondary latex for the three grades of carbon black described above. The results show that while the morphology of carbon black influences the maximum charge that can be achieved while simultaneously producing coherent clot, the use of secondary latex provides a clear and consistent improvement in achievable loading. Dehydration The masterbatch kernel discharged from the clot reactor was dehydrated at 10-20% humidity with a dehydration extruder (The French Oil Machinery Company). In the extruder, the masterbatch core was compressed, and water extracted from the core was ejected through a grooved drum from the extruder. Drying and cooling The dehydrated clot was left in a continuous mixer (Farrel continuous mixer (FCM), Farrel Corporation) where it was ground and mixed with 1 phr of antioxidant (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylene diamine (6PPD, Flexsys, St. Louis, MO). The moisture content of the crushed masterbatch exiting the FCM was about 1-2%. The crushed masterbatch was further crushed and cooled in an open mill to form an elastomer composite. The actual levels of carbon black charge have been Petition 870190100968, of 10/08/2019, p. 51/69 45/62 determined by nitrogen pyrolysis (values listed in Tables 2A-2E) or TGA (values listed in Table 2F) in dry product. The dry elastomer composite was vulcanized; the mechanical properties of the vulcanized elastomer composite (eg tan Delta, stress ratio at 300% and 100% stress) exhibited a load variation similar to that of the vulcanized elastomer composites with smaller filler loads and prepared using the same techniques , but without secondary latex. The use of secondary latex injection allows the manufacture of more highly loaded elastomer composites without sacrificing the performance of the final rubber composites. EXAMPLE 2 Preparation of filling suspension Silica-treated carbon black (CRX TM 2000 ECOBLACK® silicon-treated carbon black, available from Cabot Corporation) is mixed with water and ground to form a suspension with a concentration of about 1015% by weight. The suspension is fed to a homogenizer at an operating pressure of about 3000 psig (20.68MPa) to produce a finely dispersed carbon black suspension, and the suspension is introduced as a jet into the mixing zone. The suspension flow rate is adjusted to about 690-960 kg / h (wet basis) to modify the final fill load levels in composites produced with field latex and up to about 1145 kg / h (wet basis) when latex concentrate is used. Primary Latex Release Or field latex with a dry rubber content of about 27-31% or natural rubber latex concentrate Petition 870190100968, of 10/08/2019, p. 52/69 46/62 is pumped into the mixing zone of the clot reactor. The latex flow rate is adjusted between about 320-790 kg / h (wet basis), in order to modify the final fill load levels. Filling and latex mix The filler suspension and latex are mixed by dragging the latex into the filler suspension in a mixing part (for example, mixing portion 10) of a clot reactor similar to that shown in Figure 1. During the dragging process, the filler material is intimately mixed in the latex and the mixture coagulates. Downstream of the mixing portion, a diffuser portion has a series of sections, each with a progressively larger diameter than the previous section, with a beveled transition portion between sections. Secondary latex release Field latex is pumped into the suspension suspension and latex coagulation mixture at the transition between the first and second sections (for example, 20a in Figure 1) at a pressure of 3-8 bar (0.3MPa-0, 8MPa) starting at a rate of about 80 kg / hour (wet basis). The latex is injected at a right angle to the wall of the clot reactor. The pumping rate is gradually increased to a maximum of 300 kg / h (wet basis) until the clot emerging from the diffuser displays the desired morphology. Dehydration The masterbatch kernel discharged from the clot reactor is dehydrated at 10-20% humidity with a dehydration extruder (The French Oil Machinery Company). In the extruder, the masterbatch core is compressed, and water Petition 870190100968, of 10/08/2019, p. 53/69 47/62 extracted from the core is ejected through a grooved drum of the extruder. Drying and cooling The dehydrated clot is dropped into a continuous mixer (Farrel continuous mixer (FCM), Farrel Corporation) where it is ground and mixed with 1 phr of antioxidant (N- (1,3-dimethylbutyl) -N'-phenyl-p- phenylene diamine (6PPD, Flexsys, St. Louis, MO) and 1.5 phr of a coupling agent (bis- (triethoxysilylpropyl tetrasulfide) (TESPT, Si-69, available from Evonik Industries, Essen, Germany). The moisture content of the crushed masterbatch exiting the FCM is about 1-2% The product is further crushed and cooled in an open mill to form a dry elastomer composite. EXAMPLE 3 Preparation of filling suspension A mixture of carbon black and silica (carbon black N234, available from Cabot Corporation, and HiSil® 233 silica, available from PPG Industries, Pittsburgh, PA) is mixed with water and ground to form a suspension with a concentration of about 10-15% by weight, with the ratio of carbon black to silica ranges from 60:40 to 80:20, by weight. The suspension is fed to a homogenizer at an operating pressure of about 3000 psig (20.68MPa) to produce a finely dispersed carbon black suspension, and the suspension is introduced as a jet into the mixing zone. The suspension flow rate is adjusted to around 690-960 kg / h (wet basis) to modify the final fill load levels in composites produced with field latex and up to about Petition 870190100968, of 10/08/2019, p. 54/69 48/62 1145 kg / h (wet basis) when latex concentrate is used. Primary Latex Release Either field latex with a dry rubber content of about 27-31% or natural rubber latex concentrate is pumped into the mixing zone of the clot reactor. The latex flow rate is adjusted between about 320 and 790 kg / h in order to modify the final fill load levels. Latex blend and filler The filler suspension and latex are mixed by dragging the latex into the filler suspension in a mixing portion (for example, mixing portion 10) of a clot reactor similar to that shown in Figure 1. During the dragging process , the filling material is intimately mixed in the latex and the mixture coagulates. Secondary latex release Field latex is pumped into the suspension suspension and latex coagulation mixture at the transition between the first and second sections (for example, 20a in Figure 1) at a pressure of 3-8 bar (0.3 to 0, 8MPa) starting at a rate of about 80 kg / hour (wet basis). The latex is injected at a right angle to the wall of the clot reactor. The pumping rate is gradually increased to a maximum of 300 kg / h (wet basis) until the clot emerging from the diffuser displays the desired morphology. Dehydration The masterbatch kernel discharged from the clot reactor is dehydrated at 10-20% with moisture from a dehydration extruder (The French Oil Machinery Company). At Petition 870190100968, of 10/08/2019, p. 55/69 49/62 extruder, the masterbatch core is compressed, and water extracted from the core is ejected through a grooved drum of the extruder. Drying and cooling The dehydrated clot is dropped into a continuous mixer (Farrel continuous mixer (FCM), Farrel Corporation) where it is ground and mixed with 1 phr of antioxidant (N- (1,3-dimethylbutyl) -N'-phenyl-p- phenylene diamine (6PPD, Flexsys, St. Louis, MO) and 1.5 phr of a coupling agent (bis- (triethoxysilylpropyl tetrasulfide) (TESPT, Si-69, available from Evonik Industries, Essen, Germany). The moisture content of the crushed masterbatch coming out of the FCM is about 1-2% The product is further crushed and cooled in an open mill to form a dry elastomer composite. EXAMPLE 4 Dry carbon black (N234, obtained from Cabot Corporation) was mixed with water and ground to form a suspension with a concentration of about 10-15% by weight. The suspension was fed to a homogenizer at an operating pressure of about 3000 psig (20.68MPa) to produce a finely dispersed carbon black suspension, and the suspension was introduced as a jet into the mixing zone. The flow rate of carbon black (dry basis) is specified in Table 4, below. Primary Latex Release Field latex with a dry rubber content of about 27-31% was pumped into the mixing zone of the clot reactor. The release rate of primary rubber (dry rubber base) in the mixing zone is listed in Table 4, Petition 870190100968, of 10/08/2019, p. 56/69 50/62 below. Mixture of carbon black and latex The carbon black and latex suspension were mixed by dragging the latex into the carbon black suspension in a mixing portion (for example, mixing portion 10) of a clot reactor similar to that shown in Figure 1. During the process of drag, the carbon black was intimately mixed in the latex and the mixture coagulated. Secondary latex release Field latex was pumped into the diffuser portion downstream, from the clot reactor in the transition between the first and second sections of the diffuser (for example, 20a in Figure 1), and the α angle (see Figure 2) was 7 degrees. The length of the first section of the diffuser (for example, 18a in Figure 1) was varied between 4 and 8.5 inches (0.10 to 0.21m); the resulting residence time before the introduction of the secondary latex flow is listed in Table 4, together with the secondary rubber release rate (dry rubber base). The corresponding residence time for the Comparative Example (that is, the residence time in the first section of the diffuser) was 1.8 x 10 -2 s. The pumping rates of primary and secondary latex and carbon black suspension were adjusted to achieve a production rate of 450-500 kg / h (dry basis). Petition 870190100968, of 10/08/2019, p. 57/69 51/62 Example Comparative example 4-1 4-2 4-3 4Λ 4-5 4-6 Black flow rate of! carbon (kg'h, dry basis) 153 167 197 192 197 195 195 Flow rate of primary rubber (kg / dry rubber base) 222 189 209 194 221 186 259 Secondary rubber flow rate (kg / dry rubber base) 0 64 61 66 67 92 42 Residence time before 2 D Elastomer - 1.8 1.9 2.4 3.0 2.4 2.2 2 D elastomer. · 'Total elastomer (%) 0 25.2 22.5 25.4 23.3 33.3 13.9 CB load measured(phrj 64.5 64.4 65.3 68 64.4 65.6 63.2 Table 4 The results of Examples 4-1, through 4-4 are shown in Figure 4. Figure 4 clearly shows an optimum residence time for maximizing fill load. This maxim is consistent with the theory described above. According to the theory, the introduction of the secondary latex flow prior to substantial decoration of the latex particles causes the rubber particles in the secondary latex stream to also become decorated, rather than bonding the rubber-fill aggregates together, while the secondary latex stream is not completely mixed with the coagulation mixture if it is introduced too far downstream. In Examples 4-5 and 4-6, the injection rate of the secondary rubber flow was varied, maintaining a residence time similar to that of Example 43. The results are consistent with the theory described above; only a certain amount of secondary latex is needed to bond discrete rubber aggregates together into a coherent clot, and latex Petition 870190100968, of 10/08/2019, p. 58/69 Additional secondary 52/62 only dilutes the final product load. Dehydration The masterbatch kernel discharged from the clot reactor was dehydrated at 10-20% humidity with a dehydration extruder (The French Oil Machinery Company). In the extruder, the masterbatch core was compressed, and water extracted from the core was ejected through a grooved drum from the extruder. Drying and cooling The dehydrated clot was left in a continuous mixer (Farrel continuous mixer (FCM), Farrel Corporation) where it was ground and mixed with 1 phr of antioxidant (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylene diamine (6PPD, Flexsys, St. Louis, MO). The moisture content of the crushed masterbatch exiting the FCM was about 1-2%. The product was further crushed and cooled in an open mill to form a dry elastomer composite. The actual carbon load levels were determined by TGA on the dry elastomer composite and are listed in Table 4. The dry elastomer composite has been vulcanized; the mechanical properties of the vulcanized elastomer composite (eg Tan Delta, ratio stress levels at 300% and 100% tension) exhibited a variation with a load similar to that of vulcanized elastomers with Secondary latex injection allows the manufacture of more highly loaded elastomer composites without sacrificing the performance of the final rubber compounds. Petition 870190100968, of 10/08/2019, p. 59/69 53/62 EXAMPLE 5 This example demonstrates improvements in the properties of vulcanized rubber compositions prepared with high volume fractions of carbon black elastomers prepared according to exemplary embodiments of the invention, compared to the already improved properties of vulcanized rubber compositions based on elastomer composites having a lower volume fraction of carbon black prepared by a wet mixing method used in Example 4 to prepare control samples and for vulcanized rubber compositions prepared by dry mixing. Preparation of masterbaches Masterbaches A were prepared according to Example 1, as follows: - Masterbatch A1 corresponds to N234, measured CB load of 66.1 phr, from Table 2D, - Masterbatch A2 corresponds to Megro Experimental 1, CB load measured at 59 phr, from Table 2F, - A3 Masterbatch corresponds to N134, measured CB load of 64.4 phr, from Table 2F Masterbatches B were prepared with the same carbon black and the same field latex according to the wet mixing method used in Example 4 to prepare the control samples, as follows: - B1 Masterbatch includes 50 phr in N234, - B2 Masterbatch includes 49 phr in Experimental Black 1, - Masterbatch B3 includes 50 phr in N134, Preparation of rubber compositions The tests that follow are performed as follows Petition 870190100968, of 10/08/2019, p. 60/69 54/62 way: the dienic elastomer and reinforcement filler or masterbatches including dienic elastomers and reinforcement fillers were introduced in an internal mixer, 70% filled and having an initial vessel temperature of approximately 50 ° C, followed, after mix for one minute, using various other ingredients, except the primary sulfur and sulfenamide accelerator. Thermomechanical work (non-productive phase) was then carried out in one or two stages (total mixing duration equal to about 5 min), until a maximum temperature drop of about 165 ° C was achieved. The mixture thus obtained was recovered and cooled and, afterwards, sulfur accelerator and sulfenamide were added in an external mixer (homofinalizer) at 30 ° C, the combined mixture was mixed (productive phase) for 3 to 4 minutes. The compositions were subsequently calendered either in the form of plates (thickness 2 to 3 mm), for the measurement of their physical or mechanical properties. Rubber compositions Rubber compositions from CA1 to CA3 and from CB1 to CB3 were produced with masterbatches from A1 to A3 and from B1 to B3, respectively. Comparative rubber compositions of CD1 to CD3 and CE1 to CE3 were manufactured using a dry mixing process from the same dry carbon blacks and solid natural rubber. Thus, all compositions included 100 phr of natural rubber (whether introduced in the form of a masterbatch or in a solid form) and different grades of carbon black, as shown in Table 5. Petition 870190100968, of 10/08/2019, p. 61/69 55/62 Table 5 Composition CD1 CB1 CE1 FALLS CD2 CB2 CE2 CA2 CD3 CB3 CE3 CA3 N234 (phr) 50 50 66 66.1- - - - - - - Experimental iniental black1 (phr) - - - - 49 49 59 59 - - - - N134_ - - - - - - - - 50 50 64 64.4 All of these compositions also include the additional ingredients shown in Table 6 Table 6 Ingredients Quantity (phr) 6PPD 2.0 Stearic acid 2.5 ZnO 3.0 CBS * (accelerator) 1.2 Sulfur 1.2 * N-cyclohexyl-2-benzothiazolsulfenamide (Flexsys: Santocure CBS) Characterization of rubber compositions The diene rubber compositions were characterized before and after curing, as indicated below. 1. Mooney plasticity An oscillating consistometer was used as described in the French standard NF T 43-005 (1991). The measurement of Mooney plasticity was carried out according to the following principle: the composition in the raw state (that is, before curing) was molded in a cylindrical chamber heated to 100 ° C. After preheating for one minute, the rotor was rotated inside the test sample at 2 Petition 870190100968, of 10/08/2019, p. 62/69 56/62 revolutions / minute and the working torque to maintain this movement was measured after the rotation for 4 minutes. Mooney's plasticity (ML 1 +4) is expressed in Mooney's unit (MU, with 1 MU = 0.83 Newton.meter). 2. Dispersion In a known way, the rubber matrix filling dispersion can be represented by the Z value, which was measured, after crosslinking, according to the method described by S. Otto and Al in Kautschuk Gummi Kunststoffe, 58 Jahrgang, NR 7- 8/2005, article entitled New Reference value for the description of filler dispersion with the dispergrader 1000NT, according to ISO 11345. The calculation of the Z value is based on the percentage of non-dispersed area, as measured by the disperGRADER + device supplied with its procedure and its operating software disperDATA by Dynisco company according to the equation: Z = 100 - (percentage of area not dispersed) / 0.35 The percentage of undispersed area was measured using a camera with a light source at an angle of 30 ° to the observation surface. Light points are associated with filler material and agglomerates, while the dark background is associated with a rubber matrix; numerical treatment transforms the image into a black and white image, and allows the determination of the percentage of non-dispersed area, as described by S. Otto in the document mentioned above. The higher the Z value, the better the dispersion of the filler material in the rubber matrix (a Z value of 100 corresponding to the perfect mixture and a Z value of Petition 870190100968, of 10/08/2019, p. 63/69 57/62 for the worst mix) 3. Rheology The measurements were carried out at 150 ° C with an oscillating disc rheometer, according to DIN 53529 - part 3 (June 1983). The change in rheometric torque as a function of time describes the change in the stiffness of the composition as a result of the vulcanization reaction. The measurements are processed according to DIN 53529 - part 2 (March 1983): ti is the induction period, that is, the time required for the vulcanization reaction to start; t α (for example t90) is the time required to achieve a conversion of α%, that is, α% (for example 90%) of the difference between the minimum and maximum torques. The constant conversion rate, denoted K (expressed in min -1 ), which is first order, calculated between 30% and 80% conversion, which makes it possible to assess the vulcanization kinetics, was also measured. 4. Traction tests These tensile tests make it possible to determine the stresses and elastic properties at break. Unless otherwise stated, they were performed in accordance with the French standard NF T 46-002 of September 1988. The nominal secant modules (or apparent stresses, in MPa) were measured in second elongation (that is, after an accommodation cycle for the degree of extension expected for the actual measurement) at 10% elongation (denoted M10), 100% elongation (denoted M100) and 300% elongation (denoted M300). The properties measured before and after curing at 150 ° C for 40 minutes are given in Tables 7, 8 and 9 Petition 870190100968, of 10/08/2019, p. 64/69 58/62 (each table corresponding to a specific degree of carbon black). C * 1 (N 36 143 cn mO QS oofl · T— CEls ! 1—1O□ The r] Γ41— ^ Π1 tjj-I(ΛOCB1OO ΡΩÜO Ooc (N esΠΊ 'TT CD1í > n O*The MD RJ o rí The7 --- í *r ô ürt ώí u Properties before curing Dc o o s Curing properties i Ή ·XH c ε rclCJL / l o&fuL / l rijhard 1 N73 G O ΓΩs O o2o o <* Ί Petition 870190100968, of 10/08/2019, p. 65/69 59/62 CS *edcn1Tj Oη if x> The is CA2onlyVJj Oso oo O CM CE2OOONLY O©un ooCT1 CM Ç ed<*! PM the rq! n fS GO fM QQUΠΊCM m lolO cn m Γ4SH+ (NQCJΌo-, W1 the 3rdSin only theCMComposition: (withExperimental Black 1) edBed njl / l Iljl / l4J ’ϋedu f£ □S'c o o s ed £ CJIlj naL / lTJ edna4jl £ c £ ed bUedl / l O &L / l υ nded ndUj f N 4J Ό 7 3 * 5 ** · —Τ · o o c *> §so c flΞ Petition 870190100968, of 10/08/2019, p. 66/69 60/62 CS 'CD oe Ort © Hey 22 <OOyp OCt &-B * x σΊ til UO'un o T- - o00«Ί80HI CS 'Π1laughs m r <t- CB3ΓΛΤΓ OÜO νΊHi HI mQU OO Hi hi O ír 2 o; π1 tf O t U - cd u g l / lul / l u cd u 1l · -1 Plh □£o o s CD* 3 uU TJl / l U tJcd TJ,dJlPh £H tí e nibiCJniL / l O &l / l iUCD0J! | -i PLd Nu73 £g m s §Ξ• - ^o o mΞ Petition 870190100968, of 10/08/2019, p. 67/69 61/62 It can be seen that all the compositions prepared by a wet mixing method (CA1 to CA3 and CB1 to CB3), when compared to compositions having the same ingredients, but prepared by the dry mixing method (from CD1 to CD3 and from CE1 to CE3), showed an improvement of all the properties mentioned above: dispersion (shown by the value of Z), processability (Mooney), rheometry (T99 and K) and reinforcement (M300 and M300 / M100). Thus, the greater the carbon black charge provided by the processes of the invention preserves the improvements obtained by wet mixing, a mechanical coagulation method of the type described in U.S. Patent No. 6,048,923. In addition, when comparing composites prepared by a wet mixing method with those prepared by a dry mixing method, the percentage of improvement obtained in high carbon black charges is, for all the properties discussed above, higher than that obtained with lower carbon black charges. The foregoing description of preferred embodiments of the present invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Modifications and variations are possible in light of the above teachings, or can be acquired from the practice of the invention. The modalities have been chosen and described in order to explain the principles of the invention and its practical application to allow an expert in the art to use the invention in various modalities and with various modifications that are suitable for the particular contemplated use. The scope of the invention is intended to be Petition 870190100968, of 10/08/2019, p. 68/69 62/62 defined by the appended claims and their equivalents.
权利要求:
Claims (15) [1] 1. Method of production of a coagulated latex composite characterized by comprising: flowing a coagulation mixture of a first elastomer latex comprising a first elastomer and a particulate filler suspension along a conduit; and introducing a second elastomer latex comprising a second elastomer into the flow of the coagulation mixture. [2] Method according to claim 1, characterized in that it further comprises, before flowing the coagulation mixture, generating the coagulation mixture by feeding a continuous flow of the first elastomer latex to a mixing zone of a clot reactor defining an elongated clot zone extending from the mixing zone to a discharge end and comprising the conduit, and feeding a continuous flow of a fluid comprising particulate pressure under pressure into the mixing zone of the clot reactor to form the mixture coagulation. [3] 3. Method according to claim 2, characterized in that the continuous flow of the fluid comprising particulate filling has a speed of 30 m / s to 250 m / s, the continuous flow of the first elastomer latex having a speed of, at most 10 m / s and a residence time of coagulation clot in the reactor mixture prior to the introduction of the second elastomer latex is 1x10 -2 6x10 -2 s sa. [4] 4. Method, according to any of the Petition 870190036496, of 16/16/2019, p. 71/77 2/4 claims 1 to 3, characterized in that the conduit comprises a first conduit portion having a first diameter, a second conduit portion having a second diameter larger than the first diameter, and a transition zone between them having a diameter that increases from the first diameter to the second diameter, where the flow comprises flowing the coagulation mixture into the second conduit portion from the first conduit portion, and the introduction comprises introducing the second elastomer latex into the mixture coagulation in the transition region. [5] 5. Method according to claim 4, characterized in that flowing the coagulation mixture comprises flowing the coagulation mixture through the transition region, under turbulent flow conditions. [6] Method according to any one of claims 1 to 5, characterized in that the amount of the second elastomer in the composite is from 0.5% by weight to 50% by weight, preferably from 16% by weight to 38% by weight . [7] Method according to any one of claims 1 to 6, characterized in that the second elastomer is a synthetic elastomer or natural rubber latex. [8] Method according to any one of claims 1 to 7, characterized in that the particulate filler comprises a carbon black with a surface area of at least 95 m 2 / g, measured by the STSA and an adsorption of dibutyl phthalate at least 80 ml / 100g, and the coagulated latex composite comprises at least 65 phr of carbon black. Petition 870190036496, of 16/16/2019, p. 72/77 3/4 [9] Method according to any one of claims 1 to 7, characterized in that the particulate filler comprises a carbon black with a surface area of at least 68 m 2 / g, measured by the STSA and an adsorption of dibutyl phthalate at least 60 ml / 100g, and the coagulated latex composite comprises at least 70 phr carbon black. [10] Method according to any one of claims 1 to 7, characterized in that the particulate filler comprises a carbon black with a dibutyl phthalate adsorption of at least 60 ml / 100g, in which the carbon black has an area surface and is present in the coagulated latex composite in an amount satisfying L> -0.26 * S + 94, where L is the amount of carbon black in the coagulated latex composite in parts per hundred of rubber (phr) and S is the surface area in m 2 / g, measured by STSA. [11] 11. Elastomer composite characterized by being formed by the method, as defined in any one of claims 1 to 10, wherein the amount of the particulate filler is 55 to 100 parts per hundred of rubber by weight. [12] Method according to any one of claims 1 to 10, characterized in that the flow of the coagulation mixture has a first degree of turbulence; and the method further understand, before introducing the second elastomer latex, to cause the first degree of turbulence to change to a second degree of turbulence, in which the introduction of the second elastomer latex into the clot occurs in a place where the clot flow have the Petition 870190036496, of 16/16/2019, p. 73/77 4/4 second degree of turbulence. [13] 13. Apparatus suitable for carrying out the method, as defined in claim 1, said apparatus comprising a clot reactor having a mixing portion and a generally tubular diffusing portion extending with the progressive increase of the cross-sectional area from one end inlet to an open discharge end, the apparatus further characterized by a release tube ending in an injection orifice adapted and constructed to release a fluid to the diffusing portion of a portal disposed between the inlet end and the open discharge end . [14] 14. Apparatus according to claim 13, characterized in that the diffusing portion comprises: a first diffuser section having a first diameter; a second diffuser section having a second diameter, the second diameter being larger than the first diameter; and a transition region between said first and second sections and having a diameter that increases from the first diameter to the second diameter, in which the portal is arranged in the transition region. [15] Apparatus according to claim 14, characterized in that it further comprises at least one additional diffuser section disposed downstream of the second diffuser section and having a larger diameter than the second diameter; at least one additional diffusing section disposed between the mixing portion and the first diffusing portion, and having a smaller diameter than the first diameter, or both.
类似技术:
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同族专利:
公开号 | 公开日 WO2011034585A3|2011-08-04| TW201120106A|2011-06-16| JP2013505324A|2013-02-14| US20120172492A1|2012-07-05| EP2478043A2|2012-07-25| CA2773599A1|2011-03-24| EP2478043A4|2014-07-23| TW201113331A|2011-04-16| WO2011034589A3|2011-08-18| IN2012DN02286A|2015-08-21| JP5833008B2|2015-12-16| JP2013505326A|2013-02-14| TWI601790B|2017-10-11| TWI443129B|2014-07-01| CN102741339B|2014-01-29| CN102630238A|2012-08-08| US9156955B2|2015-10-13| EP2478043B1|2017-10-18| EP2486093A4|2013-05-22| AU2010296002B2|2013-07-18| EP2486093A2|2012-08-15| CN102630238B|2016-09-14| WO2011034589A8|2012-04-26| EA201270431A1|2012-10-30| CN102741339A|2012-10-17| MY155456A|2015-10-15| WO2011034589A2|2011-03-24| WO2011034585A2|2011-03-24| MX2012003130A|2012-04-19| KR20120093219A|2012-08-22| US20150105491A1|2015-04-16| US20150337091A1|2015-11-26| US20120277344A1|2012-11-01| EP2486093B1|2016-11-16| CA2773920A1|2011-03-24| MX341018B|2016-08-04| CA2773599C|2015-12-08| KR101678718B1|2016-11-23| JP5684265B2|2015-03-11| AU2010296002A1|2012-03-29| EA026634B1|2017-04-28| BR112012008314A2|2016-03-22|
引用文献:
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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]| 2019-02-19| B06T| Formal requirements before examination [chapter 6.20 patent gazette]| 2019-07-16| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]| 2020-01-14| B09A| Decision: intention to grant [chapter 9.1 patent gazette]| 2020-02-04| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/09/2010, OBSERVADAS AS CONDICOES LEGAIS. |
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申请号 | 申请日 | 专利标题 US27687609P| true| 2009-09-17|2009-09-17| US28045309P| true| 2009-11-04|2009-11-04| PCT/US2010/002523|WO2011034589A2|2009-09-17|2010-09-16|Formation of latex coagulum composite| 相关专利
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