ELASTOMER COMPOSITION WITH RECLAIMED FILLER MATERIALS

The present invention is directed to a carrier elastomer composition having an elastomer material between about 20% to about 80% by weight of the carrier elastomeric composition. The carrier elastomeric composition also includes a fine agglomerates mixture of filler derived from pyrolyzed polymeric materials. The fine agglomerates mixture of filler comprises between about 10% to about 70% by weight of the carrier elastomeric composition. The carrier elastomeric composition also has a processing oil that is present in a quantity of about 25% to about 30% by weight of the carrier elastomeric composition. The carrier elastomeric composition in accordance with the present invention serves as a carrier for transporting the fine agglomerates mixture which includes agglomerate having an average particle size equal to or less than 35 nm.

Skip to: Description  ·  Claims  · Patent History  ·  Patent History
Description
CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of the following applications:

    • U.S. Provisional Application No. 60/986,126, filed Nov. 7, 2007.
    • U.S. Provisional Application No. 60/998,197 filed Oct. 9, 2007.
    • U.S. Provisional Application No. 60/986,318 filed Nov. 8, 2007.
    • U.S. Provisional Application No. 60/986,369 filed Nov. 8, 2007.

The disclosures of the above applications are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to an elastomer composition including reclaimed filler materials.

BACKGROUND OF THE INVENTION

In the rubber industry, rubber products such as vehicle tires and seals are made typically by compounding a mixture of fillers, such as carbon black or silica in rubber, which is then vulcanized. For vehicle tires, additional structural properties are introduced by embedding cords and by using different types of rubber in the tread, side-wall, and interior lining.

The manufacturer of rubber materials, such as a tire manufacturer, typically receives a raw material from different sources. Rubber is received in bales or possibly as a crumb or a powder. In making the rubber, filler materials such as carbon black are used. The carbon black that is most desirable for use as a filler in rubber compounds, including tires, in its original or “virgin” state is called fluffy carbon black. Fluffy carbon black is carbon black material that has been refined into fine particles or agglomerates that are measured in nanometers (nm) and have a very low bulk density. There are several processes for making carbon black, including an oil furnace process. The oil furnace process is typically used for making carbon black, and in many of these processes, filler is made called fluffy carbon black. More recently there has been greater interest in producing carbon black-like fillers from used rubber products such as scrap tires. Such processes essentially allow for reclaimed carbonaceous materials which include carbon blacks and other fillers to be extracted from the used rubber products and recycled back into new rubber products as filler materials.

There have been many attempts to produce fine filler from recycled tires and other rubber products from a process called pyrolysis. Through pyrolysis, tires and other oil based compounds have been processed to produce fuel and char which includes agglomerate or clusters of particles which include carbon blacks and other filler materials. Attempts have been made to use this char as a low grade carbon black for use as a type of filler. However, this has been met with several disadvantages, most significantly the disadvantage of the impurities in the char resulting from the random distribution of particle size of the agglomerates making up the filler. Additionally the surface chemistry of the particles has an effect on the performance of the filler. Thus there exists a need to provide elastomeric compounds containing fine agglomerate mixtures of carbon black and other fillers that are suitable for use as a high grade filler material comparable to virgin carbon black material. There also exists a need to “package” the fine agglomerates mixtures so that it can be transported to the customer. Additionally there is a need to “package” the fine agglomerates mixture so that it is predispersed to make it more useful when blending to make rubber compounds.

SUMMARY OF THE INVENTION

The present invention is a method for producing an elastomer composition with reclaimed filler materials.

The present invention is directed to an elastomer composition having an elastomer material between about 20% to about 80% by weight of the carrier elastomeric composition. The carrier elastomeric composition also includes a fine agglomerates mixture of filler derived from pyrolyzed polymeric materials. The fine agglomerates mixture of filler comprises between about 10% to about 70% by weight of the carrier elastomeric composition. The carrier elastomeric composition also has a processing oil that is present in a quantity of about 25% to about 30% by weight of the carrier elastomeric composition. The carrier elastomeric composition in accordance with the present invention serves as a carrier for transporting the fine agglomerates mixture which includes agglomerate having an average particle size equal to or less than 35 nm. By itself the fine agglomerates mixture easily becomes airborne thus the carrier elastomeric composition in accordance with the present invention “packages” the fine agglomerates mixture in a medium for ease of transport to customers. Additionally the carrier elastomeric composition provides rubber manufacturers with a material that is predispersed with carbon black and other fillers, which is particularly advantageous to a rubber manufacturer who are often faced with the challenge of obtaining good filler dispersion throughout the compounding process. Examples of elastomer compositions in accordance with the present invention will be discussed in further detail below.

Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:

FIG. 1 is a prior art schematic view of a classification and identification apparatus;

FIG. 2 is a plan schematic view of the pulverizer mill and the flow of carbon black through it in accordance with the present invention;

FIG. 3 is a plan schematic view of the classifier in accordance with the present invention;

FIG. 4a is a microphotograph of the fine agglomerates mixture dispersed in an aqueous solution and magnified 285,650 times in accordance with the teachings of the present invention;

FIG. 4b is a microphotograph of the fine agglomerates mixture dispersed in an aqueous solution and magnified 28,650 times in accordance with the teachings of the present invention;

FIG. 5a is a microphotograph of the KHC1 aggregate dispersed in an aqueous solution and magnified 285,650 times;

FIG. 5b is a microphotograph of the KHC1 aggregate dispersed in an aqueous solution and magnified 28,650 times;

FIG. 6a is a graph illustrating the particle size distribution of the fine agglomerates mixture in accordance with the teachings of the present invention;

FIG. 6b is a graph illustrating the particle size distribution of the KHC1 sample;

FIG. 6c is a graph illustrating the particle size distribution of the KHC2 sample;

FIG. 6d is a graph illustrating the particle size distribution of the CBp0 sample;

FIG. 7 is a graph of the rheometer curves of the CBp-25-filler, N550 filler and N660 filler in EPDM in accordance with an embodiment of the present invention; and

FIG. 8 is a graph of the rheometer curves of the CBp-25-filler, N550 filler and N660 filler in SBR in accordance with an embodiment of the present invention.

 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.

The present invention is directed to a carrier elastomeric composition having a fine agglomerates mixture blended with the elastomer. The fine agglomerates mixture is a suitable filler material for use in rubber compounding. Blending the fine agglomerates mixture with the elastomer provides a way of packaging the fine agglomerates mixture in a predispersed form which makes it ideal for blending with elastomer compounds.

FIG. 1 depicts a schematic view of the identification and separation arrangement 10 in accordance with the present invention. Referring now to all of the figures and FIG. 1 in particular, the arrangement 10 includes a pulverizer mill 12 and a classifier 14. A hopper 16 serves as a source for the reclaimed carbonaceous materials to the arrangement 10. The hopper 16 is used to collect reclaimed carbonaceous materials prepared from the pyrolysis of recycled polymeric materials, such as but not limited to scrap tires, polymeric automotive components, used rubber materials, and plastic containers or the like. The reclaimed carbonaceous materials consist of large agglomerates, and small agglomerates of carbon black and other materials. While a collection hopper 16 is used to hold the reclaimed carbonaceous materials it is possible for the reclaimed carbonaceous materials to be fed directly into the arrangement 10 from a pyrolysis reactor (not shown) without first being collected in the hopper 16.

A valve 18 controls the flow of reclaimed carbonaceous materials from the hopper 16 to a magnet separator 20. The reclaimed carbonaceous materials sometimes have metal particles that were present in the recycled polymeric material prior to pyrolysis. These metal particles can harm the pulverizer mill 12 and the magnet separator 20 removes these unwanted metal particles. The use of the magnet separator 20 is not required and a greater or lesser number of magnet separators can be used.

After passing through the magnet separator 20 the reclaimed carbonaceous material is presented to a screw 22 that rotates and controls the flow of the material to the pulverizer mill 12. A valve 24 is used to turn on and off the flow of reclaimed carbonaceous material to a mixing node 26. At the mixing node 26 the reclaimed carbonaceous material is mixed with dry, filtered high pressure air generated from an air source 28. Together the mixture of dry pressurized air and reclaimed carbonaceous material are a feed that is introduced through a feed inlet 30 (see FIG. 2) of the pulverizer mill 12.

FIG. 2, depicts a schematic diagram of the pulverizer mill 12 which has a vortex column 28 where pressurized feed is introduced through the feed inlet 30 and swirls around the vortex column 28 causing the small agglomerates present in the feed to move to the top of the vortex column 28 while the larger agglomerates fall downward. While a single feed inlet 30 is described it is possible to have a greater number of feed inlets to adjust or enhance the swirling in the vortex column 28. A classifying disk 32 is present in the vortex column 28 and contributes to the swirling of the feed and prevents large agglomerates from moving past the classifying disk 22. The classifying disk 32 swirls the agglomerates and air in the vortex column 28 and uses specific gravity to separate the heavy dense agglomerates and particles from the lighter less dense agglomerates and particles. Thus the heavy dense agglomerates settle to the bottom of the vortex column 28, while the less dense agglomerates move to the top of the vortex column 28.

As the larger agglomerates move to the bottom of the vortex, they enter a fractionation chamber 34 of the pulverizer mill 12. At least two opposing air inlets 36 are present in the fractionation chamber 34 for blowing the large agglomerate particles at opposite sides of the chamber toward each other. While two opposing air inlets 36 are discussed it is possible to have a greater or lesser number of opposing air inlets 36. The large agglomerate particles are accelerated toward each other, collide and are fractionated into smaller agglomerates. The smaller agglomerates are reintroduced into the vortex column 28 where they go past the classification disk 32 if their density is low enough, and then travel out of a small agglomerates port 38. The larger agglomerates that do not get fractionated exit a chamber outlet 38 and are collected. Optionally the large agglomerates that leave via the chamber outlet 38 can be reintroduced to the reclaimed carbonaceous material at the valve 24.

The small agglomerates that pass through the small agglomerates port 38 flow on to one of two filter hoppers 40, 40′. The filter hoppers contain a polymer surface area filter that collects the small agglomerates which have a tendency to become airborne after leaving the vortex column 28. The present invention describes using two filter hoppers for collecting the small agglomerates, however, it is within the scope of this invention for a greater or lesser number of filter hoppers to be used depending upon the rate of production from the pulverizer mill 12. Valves 42, 42′ control the flow of small agglomerates from the filter hoppers 40, 40′ onto a small agglomerate supply hopper 44 that is used to supply small agglomerates to the classifier 14. While FIG. 1 depicts multiple valves 42, 42′ associated the filter hoppers 40, 40′ it is possible to have a greater or lesser number of valves. After leaving the small agglomerate supply hopper 44 the small agglomerates are optionally passed through a second magnet filter 46 to further remove any metallic impurities present. A feed screw 48 receives the small agglomerates and controls the flow of small agglomerates supplied to a conveyor 50 that moves the small agglomerates to another feed screw 52 and valve 54 that control the flow of the small agglomerates to the classifier 14. It is with the scope of this invention to have the feed screw 48 flow directly to the classifier 14, however, it is preferable to use multiple feed screws and the conveyor because of the physical size of the components in the identification and separation arrangement 10 requires moving the small agglomerates a distance between components.

Referring now to FIGS. 1 and 3 the small agglomerates enter the classifier 14 through the one of two high pressure inlets 66. The small agglomerates are mixed with dry pressurized air, fed through one of the two inlets 66 and are swirled in a vortex column 56 of the classifier 14 where the small agglomerates are separated into a coarse agglomerates mixture and a fine agglomerates mixture. Some of the small agglomerates are made of coarse agglomerates with fine agglomerates stuck to the coarse agglomerates. The swirling of the small agglomerates causes the fine agglomerates which have a low density and are sized in the nanometer range to separate from the coarse agglomerate particles which are much more dense and are measured in microns. The swirling action in the vortex column 56 is caused by the air pressure flowing through the high pressure inlets 66 and a rotary classification wheel 58 which causes the fine agglomerates which are less dense and have a smaller particle size to move to the top of the vortex column 56. The coarse agglomerates which are more dense and generally larger in size than the small agglomerates move to the bottom of the vortex column. It is within the scope of this invention to have a greater or lesser number of air inlets 66 as well as having the small agglomerates enter the vortex column 56 through more than one of the high pressure inlets 66.

The rotary classification wheel 58 functions in the same way as the classification disk 32 of the pulverizer mill 12 by only allowing agglomerates of a certain size and density to pass out of the vortex column 58 through a fine agglomerates outlet 64. The coarse agglomerates settle to the bottom of the vortex column 56 and are collected in a container 62 for use as a filler in processes where coarse agglomerates are acceptable. The fine agglomerates that pass through the fine agglomerates outlet 64 flow to a filter hopper 68 containing a polymeric surface area filter that collects the fine agglomerates. This step is necessary because the fine agglomerates are so small in size that they become easily airborne. After passing through the filter hopper 68 the fine agglomerates are then optionally passed through a magnet separator 70 to remove any metallic impurities that might be present and then the fine agglomerates are moved to a holding area 72 where they form a fine agglomerates mixture that is stored in a container, pelletizer, bag or blended with an elastomer to prevent the fine agglomerates from becoming airborne. The fine agglomerates mixture and coarse agglomerates mixture contain high amounts of carbon black and are useful filler materials that are comparable to virgin carbon blacks.

The fine agglomerates mixture in the holding area 72 are clusters of particles that include carbon black particles in accordance with the present invention. The fine agglomerates mixture is formed from the pyrolysis of polymeric materials such as tires, polymeric automotive components, recyclable polymeric components such as milk cartons and other containers, asphalt or any other suitable source of polymeric material that will yield fine agglomerates suitable for use as fillers in rubber compounding processes. The fine agglomerates mixture includes a carbon content of generally about 80% to about 95%; typically about 85% to about 90%, preferably about 89% to about 91%, and about 90% by weight of the fine agglomerates mixture in a preferred embodiment of the invention.

The average agglomerate size of the fine agglomerates mixture is less than or equal to 4 microns and are formed from clusters of fine agglomerate particles averaging less than or equal to 35 nm when dispersed in an aqueous solution and measured using electron microscopy. The size of the fine agglomerate particles is important from the standpoint that the smaller the agglomerate size the better they are for use as a high grade filler comparable to a N500 to N600 grade virgin carbon blacks.

The nitrogen surface area of the fine agglomerates mixture is another important factor in determining whether a filler material will be suitable as a high grade filler material. The nitrogen surface area is indicative of the binding affinity the filler material has when used in rubber compounding. The fine agglomerates mixture of the present invention generally has nitrogen surface areas that area measured using two different techniques, the BET technique and the Iodine absorption technique. The fine agglomerates mixture has a nitrogen surface area determined using the BET technique of generally about 46 m2/g to about 72 m2/g and preferably about 58 m2/g. The fine agglomerates mixture has a nitrogen surface area determined using the iodine absorption technique of about 53 mgl2/g to about 254 mgl2/g and preferably about 176 mgl2/g.

The fine agglomerates mixture also has pyrolyzed carbon black particles and inorganic functional filler material which after treatment by the separation and identification apparatus allows for the fine agglomerates mixture to function like a commercial carbon black having an N500 to N600 rating. The inorganic functional filler can be one selected from the following group; silica, alumina, titania, iron oxide, calcium oxide, magnesium or combinations thereof. It is also possible for other inorganic filler materials to be used provided that they allow for the fine agglomerates mixture to function like a desired grade of virgin carbon black. The present invention has functional inorganic fillers that are generally about 5% to about 20%; and typically about 8% to about 15% and preferably about 9% to about 11%; and in a preferred embodiment of the invention about 10% by weight of the fine agglomerates mixture.

Fine agglomerates mixtures are obtained using the identification and separation apparatus 10. In accordance with the present invention the carrier elastomeric composition is prepared using the fine agglomerates mixture as a filler that is derived from pyrolyzed polymeric materials. A carrier elastomeric composition in accordance with the present invention includes an elastomer material that is generally about 20% to about 80%; typically about 15% to about 30% of the weight of the carrier elastomeric composition, preferably about 19% to about 21% and in a preferred embodiment about 20% of the weight of the carrier elastomeric composition. The elastomeric material can include Styrene Butadience Copolymer (SBR), Ethylene Propylene Diene M-class rubber (EPDM), nitrile elastomers, butyl elastomers, natural rubber and combinations thereof. It is also within the scope of the present invention for the elastomeric material to be virtually any type of synthetic or natural elastomer used within the rubber industry.

The carrier elastomeric composition also includes a fine agglomerates mixture of filler that is generally about 10% to about 70% by weight of said carrier elastomeric composition; typically about 40% to about 60% of the weight of the carrier elastomeric composition, preferably 52% to about 57% and in a preferred embodiment of the invention about 55% of the weight of the carrier elastomeric composition. The fine agglomerates mixture is derived from pyrolyzed polymeric materials which include polymeric automotive components such as tires, and other automotive plastics which yield a suitable amount of carbon black for pyrolysis. The polymeric materials can also include recyclable polymeric materials which are derived from non-automotive sources and can include pulverized asphalt, plastic containers or any other suitable polymeric material that would yield a sufficient amount of carbon black. The carrier elastomeric composition also has a processor oil that is generally about 25% to about 30% of the weight of the carrier elastomeric composition; typically about 25% to about 30% of the weight of the carrier elastomeric composition and preferably about 23% to about 27% and in a preferred embodiment of the invention about 25% of the weight of the carrier elastomeric composition. The processing oil can be any suitable oil that aids in mixing the fine agglomerates mixture with the elastomer material. One example of a processing oil is Sunthene® 4240 produced by Sunoco Oil Company, Tulsa, Okalahoma; United States of America; however, any other suitable processing oil can be used depending on the needs of a particular application.

In addition to the above carrier elastomeric compositions which include an elastomeric material fine agglomerates mixture and processing oil, there are also several other optional components that can be added depending upon the needs of a particular application of the present invention. Certain embodiments of the present invention may also include processor aids, activators, anti-oxidants and other filler materials as well as combinations of each of these groups. The processing aids help to improve the blending of the carrier elastomeric composition by preventing sticking to the mixing components and improve disbursion of the elastomer material, reclaim carbonaceous mixture of filler and processing oil. The processing aids can include zinc soaps, fatty acid salts and combinations thereof as well as any other suitable or desired processing or known processing aids.

It is also optional to add activators to the above carrier elastomeric composition. The activators serve to accelerate curing of the carrier elastomeric composition during vulcanization. Activators can include zinc oxide stearic acid and silanes (particularly when silica fillers are present), and combinations thereof. It is also within the scope of this invention for other suitable known activators to be used depending upon the needs of a particular application.

Additionally anti-oxidants can also be added to the above carrier elastomeric composition. Anti-oxidants serve to prevent hardening of the carrier elastomeric composition after curing. Known suitable anti-oxidants include phenylamines, styrenated pheols, and combinations thereof. It is also within the scope of this invention for any other known suitable anti-oxidants to be used depending upon the needs of a particular application.

It is also within the scope of this invention to include other filler materials with the above described carrier elastomeric composition. Filler materials can provide desired physical and chemical properties such as improving density, heat resistance or changing the color of the carrier elastomeric composition. Possible filler materials include whiting, calcium carbonate, silica and combinations thereof. Additionally it is also possible to include other known suitable filler materials depending upon the needs of a particular application.

Additionally other embodiments of the present invention include accelerators added to the carrier elastomeric composition. Accelerators assist in speeding up the vulcanization process. The number of accelerators is quite numerous and there are a large number of different types of accelerators that can be used in forming carrier elastomeric compositions. The selection of an accelerator to be added to the carrier elastomeric composition is dependent upon factors which in part include the manufacturer's requirements as well as other factors such as equipment, processing variables and the preference of the individual compounder. Some of the accelerators suitable for use with the present invention include groups of accelerators known as secondary accelerators such as tetramethylthiuram monosulfied which is part of a group of accelerators called thiurons. Delayed action accelerators can also be added. One suitable delayed action accelerator is N-tert-butyl-benzothiazole sulfonamide (TBBS). Another suitable accelerator includes a class known as primary accelerators that include mercaptobenzothiazole (MBT). Although specific accelerators and groups of accelerators are described above, it is within the scope of this invention for virtually any type of accelerator to be used with the carrier elastomeric composition in accordance with the present invention. Therefore the present invention is no way intended to be limited to any single type of accelerator.

Example 1

A carrier elastomeric composition is formed with an elastomer material present in generally about 20% to about 80% by weight of the carrier elastomeric composition; typically about 20% to about 30% by weight of the carrier elastomeric composition; and preferably about 19% to about 21% and in a preferred embodiment about 20% of the weight of the carrier elastomeric composition. A fine agglomerates mixture present in generally about 10% to about 70% of the weight of the carrier elastomeric composition; typically about 40% to about 55% of the weight of the carrier elastomeric composition, preferably 52% to about 57% and in a preferred embodiment of the invention about 55% of the weight of the carrier elastomeric composition. A processor oil is present in generally about 25% to about 30% weight of the carrier elastomeric composition; typically about 25% to about 30% of the weight of the carrier elastomeric composition and preferably about 23% to about 27% and in a preferred embodiment of the invention about 25% of the weight of the carrier elastomeric composition. The carrier elastomeric composition is blended such that the fine agglomerates mixture is evenly dispersed throughout the carrier elastomeric composition.

In another aspect of the invention carrier elastomeric compositions in accordance with the present invention were blended with commercial elastomer formulations and the chemical and mechanical properties were analyzed and compared with other commercial elastomer compositions using virgin carbon blacks. Additionally highly loaded commercial elastomer formulations were prepared using the carrier elastomeric compositions in accordance with the present invention which were analyzed and compared to highly loaded elastomer compositions containing virgin carbon blacks.

In the foregoing CBp-25E-filler has been used to designate the fine agglomerates that have been blended into a carrier elastomer composition in accordance with the present invention. Examples of elastomer compositions and highly loaded elastomer compositions were prepared using the CBp-25E-filler that has been previously blended into a carrier elastomer composition. Carrier elastomeric compositions were prepared by blending the fine agglomerates with Styrene Butadiene Copolymer (SBR) and Ethylene Propylene Diene M-class rubber (EPDM) which were then blended with commercial formulations using SBR and EPDM. It is also possible to use the fine agglomerates in powder or pelletized form, however, using the elastomer composition in accordance with the present embodiment of the invention allows for easier transport and better dispersion of the fine agglomerates in commercial compositions.

Example 2

Commercial elastomer compositions were formulated and tested. Table 1 set forth below lists a mixture of fine agglomerates, hereafter referred to as CBp-25E-filler blended as a commercial elastomer compound in SBR. Table 1 also shows mixtures of N550 filler and N660 filler, which are carbon black filler materials obtained from virgin carbon black sources such as crude oil pyrolysis, blended with SBR.

TABLE 1 BATCH MIXES WITH SBR CBp-25E N550 N660 SBR 1500 100.00 phr  100.00 phr  100.00 phr  CBp-25E-filler 80.00 phr  N550-filler 80.00 phr  N660-filler 80.00 phr  Zinc Oxide 3.00 phr 3.00 phr 3.00 phr Stearic Acid 1.00 phr 1.00 phr 1.00 phr Santocure TBBS 1.00 phr 1.00 phr 1.00 phr Sulphur 1.75 phr 1.75 phr 1.75 phr

As shown in the table above, the CBp-25E-filler, N550-Filler and N660-filler were all mixed with 80 per one hundred parts rubber (phr). Other ingredients were also added in equivalent proportions.

Table 2 is a table of the mechanical properties of the SBR elastomer composition samples prepared with the CBp-25E-filler, N550 filler and N660 fillers discussed above in Table 1.

TABLE 2 MECHANICAL PROPERTIES IN SBR CBp-25E- Filler N550 N660 Density [kg/l] 1.20(1.22) 1.22 1.22 Hardness [IRHD] 72(74) 77 74 Tensile strength [MPa] 22.9(23.7) 24.3 23.2 Elongation at break [%] 460(473) 310 355 Modulus 100% [MPa] 4.0(3.5) 8.0 6.1 Modulus 300% [MPa] 14.6(14.2) 24.1 21.4 Tear Strength [kN/m] 44.1(47.2) 41.3 48.3 DIN abrasion [mm3] 106(107) 80 84

As shown in Table 2 above, the density, hardness and tensile strength of the CBp-25E-filler is similar to the N550 and N660 fillers when blended with SBR in accordance with the present embodiment of the invention. The CBp-25E-filler showed a greater elongation percentage at the break point than the elastomer compositions made with the N550 and N660 filler materials. Thus, the CBp-25E-filler has a better elasticity than the natural carbon black fillers. Additionally, the other properties, such as tear strength and DIN abrasion of the CBp-25E-filler sample was also are similar to the N550 and N660 samples. Based on the above test data, the CBp-25E-filler when blended with SBR is a suitable material for formulating elastomer compounds with SBR. The mechanical properties of the CBp-25E filler are suitable, if not superior, to the natural carbon black fillers that were tested.

FIG. 8 is a graph of the rheometer curves of the three samples set forth in Table 1 above. The rheological properties of the samples is important from the standpoint of rubber manufacturing because it provides insight into how fast you can compound with the materials. In the present case the rheological properties suggest how quickly commercial elastomer compositions with SBR can be made with CBp-25E filler compared to N550 and N660 virgin carbon blacks. The rheometer measurements were taken on a MDR2000E, arc 0.5°, temperature at 170° C., elapsed time 30 min., with the torque axis at 4.0 Nm. The graph plots the torque versus time. As shown in FIG. 8, the CBp-25E filler has a similar curve to the N550 and the N660 samples. This suggests that the vulcanization time frame for compounds using CBp-25E filler is similar to mixtures using virgin carbon blacks.

Table 3 set forth below lists the measured rheological properties of each of the sample prepared with SBR. The rheometer measurements were taken on a MDR2000E, arc 0.5°, temperature at 170° C., elapsed time 30 min., with the torque axis at 4.0 Nm.

TABLE 3 RHEOLOGICAL PROPERTIES IN SBR CBp-25E- Filler N550 N660 ts2 [min] 1.34 2.46 2.42 ts90 [min] 6.88 7.96 7.64 ML [Nm] 0.40 0.54 0.39 Delta S [Nm] 1.85 2.41 2.15

The results shown in Table 3 above show that the ts2 value of the CBp-25E filler sample is lower than the N550 and N660 samples. The ts2 value indicate the initial time that the sample starts to vulcanize. Thus the CBp-25E filler is quicker to begin vulcanizing. The ts90 value indicates the time that 90% of the sample has cured. The CBp-25E filler sample reached this point quicker than the N550 and N660 samples. Thus the time to process with the CBp-25E filler is quicker. The ML measurement is the viscosity of the compound during mixing which suggests how sticky or difficult if the composition to mix which is important from the standpoint of obtaining good dispersion of all the components in the composition. The CBp-25E filler had a lower ML value than the N550 sample but a slightly higher value or nearly identical measurement to the N660 sample. The Delta S value is the slope of the curve for each of the samples in FIG. 8. This indicates how much the viscosity changes over time. In the case of the three samples measured the CBp-E25 changed the least out the three samples tested.

Example 3

Commercial elastomer compositions were formulated and tested. Table 4 set forth below lists a mixture of fine agglomerates, hereafter referred to as CBp-25E-filler blended as a commercial elastomer compound in EPDM. Table 4 also shows mixtures of N550 filler and N660 filler, which are carbon black filler materials obtained from virgin carbon black sources such as crude oil pyrolysis, blended with EPDM.

TABLE 4 Batch Mixtures in EPDM CBp-25E N550 N660 Keltan 4502 100.00 phr  100.00 phr  100.00 phr  CBp-25E-filler 70.00 phr  FEF-N550-filler 70.00 phr  GPF-N660-filler 70.00 phr  Sunpar 2280 5.00 phr 5.00 phr 5.00 phr Zinc Oxide 5.00 phr 5.00 phr 5.00 phr MBT 1.00 phr 1.00 phr 1.00 phr TMTM  1.5 phr  1.5 phr  1.5 phr Sulphur  1.5 phr  1.5 phr  1.5 phr

As shown in the Table above, the CBp-25E elastomer compound, N550 filler and N660 filler were all mixed with 70 per one hundred parts rubber (phr). Other ingredients were also added in equivalent proportions.

Table 5 is a table of the mechanical properties of the EPDM elastomer composition samples prepared with CBp-25E filler, N550 filler and N660 fillers discussed above.

TABLE 5 MECHANICAL PROPERTIES IN EPDM CBp-25E N550 N660 Density [kg/l] 1.12 1.12 1.12 Hardness [IRHD] 76 82 82 Tensile strength [MPa] 16.3 16.8 16.4 Elongation at break [%] 350 245 240 Modulus 100% [MPa] 3.8 7.0 6.1 Modulus 300% [MPa] 13.4 — — Tear Strength [kN/m] 34.6 33.3 33.1 Compression set at [%] 10 7 8 24 H@70° C.

As shown in the table above, the density, hardness and tensile strength of the CBp-25E sample is nearly identical to the N550 and N660 fillers when blended with EPDM in accordance with the present embodiment of the invention. The CBp-25E sample showed a greater elongation percentage at the break point than the elastomer compositions made with the N550 filler or N660 filler. Thus, the CBp-25E sample has a better elasticity than the natural carbon black fillers. Additionally, the other properties such as tear strength and compression percentage, of the CBp-25E sample are also similar to the N550 and N660 samples.

FIG. 7 is a graph of the rheometer curves of the three samples in the present example. The rheological properties of the samples is important from the standpoint of rubber manufacturing because it provides insight into how fast you can compound with the materials. In the present case the rheological properties suggest how quickly commercial elastomer compositions with EPDM can be made with CBp-25E filler compared to N550 and N660 virgin carbon blacks. The rheometer measurements were taken on a MDR2000E, arc 0.5°, temperature at 170° C., elapsed time 30 min., with the torque axis at 4.0 Nm. The FIG. 7 graph plots the torque versus time. As shown in FIG. 7, the CBp-25E filler has a similar curve to the N550 and the N660 samples. This suggests that the vulcanization time frame for compounds using CBp-25E filler is similar to similar mixtures using virgin carbon blacks.

Table 6 set forth below lists the measured rheological properties of each of the sample prepared with SBR. The rheometer measurements were taken on a MDR2000E, arc 0.5°, temperature at 170° C., elapsed time 30 min., with the torque axis at 4.0 Nm.

TABLE 6 RHEOLOGICAL PROPERTIES IN EPDM CBp-25E- Filler N550 N660 ts2 [min] 0.82 0.78 0.82 ts90 [min] 3.45 3.54 3.65 ML [Nm] 0.27 0.32 0.28 Delta S [Nm] 2.47 2.86 2.97

The results shown in Table 6 above show that the ts2 value of the CBp-25E filler sample is identical to the N660 sample and slightly higher than the N550 sample. The ts2 value indicate the initial time that the sample starts to vulcanize. The CBp-25E filler sample is comparable to the other samples. The ts90 value indicates the time that 90% of the sample has cured. The CBp-25E filler sample reached this point quicker than the N550 and N660 samples. Thus the time to process with the CBp-25E filler is quicker. The ML measurement is the viscosity of the compound during mixing which suggests how sticky or difficult if the composition to mix which is important from the standpoint of obtaining good dispersion of all the components in the composition. The CBp-25E filler had a lower ML value than the N550 and N660 samples. The Delta S value if the slope of the curve for each of the samples in FIG. 8. This indicates how much the viscosity changes over time. In the case of the three samples measured the CBp-E25 filler sample changed the least out the three samples tested.

Example 4

In yet another embodiment of the present invention, highly loaded elastomer compositions were prepared with CBp55% mb SBR which was an carrier elastomeric composition having 55% fine agglomerates content per weight of the carrier elastomeric composition. Such highly loaded compounds are desirable for certain rubber applications where greater amounts of filler can be used to save on material costs. For example, rubber coated metallic components as well as other applications may not require an elastomer compound that has the mechanical properties of an elastomer using a more expensive virgin carbon black filler material or equivalent thereof.

Table 7 set forth below lists one exemplary mixture of CBp55% mb SBR to form a highly loaded SBR elastomer compound.

TABLE 7 Highly Loaded Formulation with SBR-masterbatch CBpES mb-S55% 300 phr  SBR 1502 40 phr Whiting 60 phr Zinc Oxide  5 phr Stearic acid  2 phr TBBS 2.5 phr  Sulphur  2 phr Total phr 411.5 phr  

The CBpES mb-S55% elastomer compound has a fine agglomerates mixture present in the an amount of 55% of the weight of the elastomer composition. The CBp sample in this application was mixed with 300 per one hundred parts rubber (phr).

Table 8 is a table of the mechanical properties of the highly loaded SBR elastomer composition.

TABLE 8 Mechanical Properties of Cost-Efficient SBR Compound Mooney Visc. ML (1 + 4) 100° C. [MU] 37.9 Density [kg/L] 1.32 Hardness [IRHD] 63 Tensile strength [MPa] 6.7 Elongation at break [%] 555 Modulus 100% [MPa] 1.6 Modulus 300% [MPa] 4.3 Tear strength [kN/m] 85.3 Rebound resilience [%] 19

As shown in Table 8 above the mechanical properties of this sample quite different from the above samples which exhibit much different tensile strength, elongation at break values, modules 100% and 300%. However, highly loaded elastomer compounds are typically used for other types of applications such as rubber coating tools, mats, bumpers and other components where properties such as tensile strength and elongation at break are not as crucial. Instead the highly loaded elastomer composition provides a more cost efficient composition that is derived from reclaimed carbonaceous materials and reduces the need to use more costly virgin carbon blacks.

Example 5

In yet another embodiment of the present invention, highly loaded elastomer compositions were prepared with CBp60% mb EPDM which was a carrier elastomeric composition having 60% fine agglomerates content per weight of the carrier elastomeric composition. Such highly loaded compounds are desirable for certain rubber applications where greater amounts of filler can be used to save on material costs. For example, rubber coated metallic components, mats, bumpers as well as other applications may not require an elastomer compound that has the mechanical properties of an elastomer using a virgin carbon black filler material or equivalent thereof.

Table 9 sets forth a master batch mixture of the CBp-filler blended with EPDM to form a highly loaded EPDM elastomer compound.

TABLE 9 Highly Loaded Formulation with EPDM-masterbatch CBpES mbE-60% 375 phr  Dutral Ter 6148 58.8 phr  Whiting  10 phr Sunpar 2280  30 phr Zinc Oxide   5 phr Stearic acid 1.5 phr MBTS 80% 1.9 phr ZBPD 75% 3.7 phr Sulphur 80% 2.5 phr Total phr 578.4 phr 

The CBpES mbE-60% elastomer compound was a compound having fine agglomerates present in the amount of 60% of the weight of the elastomer compound. The CBp sample was mixed at 375 phr.

Table 10 set forth below show the mechanical properties of the highly loaded EPDM elastomer composition prepared using the master batch formulation set forth in Table 10 above.

TABLE 10 Mechanical Properties of EPDM Compound Mooney Visc. ML (1 + 4) 100° C. [MU] 66.1 Density [kg/L] 1.33 Hardness [IRHD] 71 Tensile strength [MPa] 5.3 Elongation at break [%] 525 Modulus 100% [MPa] 2.0 Modulus 300% [MPa] 3.9 Tear strength [kN/m] 61.4 Comp. set [72 h/70° C.] [%] 32

As shown in Table 10 above the mechanical properties of this sample quite different from the above samples which are not highly loaded. The present example when compared to the non-highly loaded elastomer compounds exhibit much different tensile strength, elongation at break values, modules 100% and 300%. However, highly loaded elastomer compounds are typically used for other types of applications such as rubber coating tools, mats, bumpers and other components where properties such as tensile strength and elongation at break are not as crucial. Instead the highly loaded elastomer composition provides a more cost efficient composition that is derived from reclaimed carbonaceous materials and reduces the need to use more costly virgin carbon blacks.

Additional information and examples of the materials used in accordance with the present invention can be found in the following applications: U.S. patent application No. 60/998,197 entitled “Elastomer Composition with Reclaimed Filler Material,” Filed Oct. 9, 2007, application No. 60/986,318 entitled “Process For Classifying Particles In A Pyrolysed Char,” filed Nov. 8, 2007, application No. 60/986,369 entitled “Asphalt Composition Using Pyrolysed Carbonaceous Materials,” filed Nov. 8, 2007, and application No. 60/986,126 entitled “Enhanced Fine Agglomerate Mixture,” filed Nov. 7, 2007, wherein the entirety of each application is hereby incorporated by reference.

The description of the invention is merely exemplary in nature and, thus, variations that do not depart from the gist of the invention are intended to be within the scope of the invention. Such variations are not to be regarded as a departure from the spirit and scope of the invention.

Claims

1. A carrier elastomeric composition comprising:

an elastomer material between about 20% to about 80% by weight of said carrier elastomeric composition;
a fine agglomerates mixture of filler derived from pyrolyzed polymeric materials between about 10% to about 70% by weight of said carrier elastomeric composition; and
a processing oil between about 25% to about 30% by weight of said carrier elastomeric composition.

2. The carrier elastomeric composition of claim 1 wherein the elastomer material is one selected from the group comprising:

styrene butadiene copolymer, ethylene propylene diene M-class rubber, nitrile elastomers, butyl elastomers, natural rubber and combinations thereof.

3. The carrier elastomeric composition of claim 1 further comprising other filler materials one selected from the group comprising:

whiting, calcium carbonate, silica, kaolin, carbonates, barites and combinations thereof.

4. The carrier elastomeric composition of claim 1 further comprising anti-oxidants one selected from the group comprising phenyl amines, styrenated phenols, and combinations thereof.

5. The carrier elastomeric composition of claim 1 further comprising activators one selected from the group comprising zinc oxide, stearic acid, silanes, and combinations thereof.

6. The carrier elastomeric composition of claim 1 further comprising one selected from the group comprising:

inorganic fillers, anti-oxidants, activators, processing aids and combinations thereof.

7. The carrier elastomeric composition of claim 1 wherein said pyrolyzed polymeric materials are derived from the pyrolysis of scrapped tires.

8. The carrier elastomeric composition of claim 1 wherein said fine agglomerates mixture of filler includes agglomerates having an average particle size of less than or equal to 35 nm.

9. The carrier elastomeric composition of claim 1 wherein said fine agglomerates mixture has a nitrogen surface area greater than or equal to 46 m2/g.

10. The carrier elastomeric composition of claim 1 wherein said fine agglomerates mixture has a nitrogen surface area greater than or equal to 53 mgl2/g.

11. The carrier elastomeric composition of claim 1 wherein said reclaimed carbonaceous material further comprises an inorganic functional filler in a range between about 5% to about 20% weight of said fine agglomerates mixture; and agglomerates having an average particle size less than or equal to 35 nm.

12. The carrier elastomeric composition of claim 1 further comprising an accelerator.

13. The carrier elastomeric composition of claim 1 further comprising a processing aid that includes one selected from the group comprising zinc soaps, fatty acid salts and combinations thereof.

14. The carrier elastomeric composition of claim 1 wherein said fine agglomerates mixture of filler includes agglomerates having an average particle size from about 10 microns to about 20 microns.

15. The carrier elastomeric composition comprising:

an elastomer material between about 20% to about 30% by weight of said carrier elastomeric composition;
a fine agglomerates mixture derived from pyrolyzed polymeric materials and forming between about 40% to about 55% by weight of said carrier elastomeric composition; and
a processing oil between about 25% to about 30% by weight of said carrier elastomeric composition.

16. The carrier elastomeric composition of claim 15 wherein the elastomer material is one selected from the group comprising:

styrene butadiene copolymer, ethylene propylene diene M-class rubber, nitrile elastomers, butyl elastomers, natural rubber and combinations thereof.

17. The carrier elastomeric composition of claim 15 further comprising other filler materials one selected from the group comprising:

whiting, calcium carbonate, silica, kaolin, carbonates, barites and combinations thereof.

18. The carrier elastomeric composition of claim 15 further comprising anti-oxidants one selected from the group comprising phenyl amines, styrenated phenols, and combinations thereof.

19. The carrier elastomeric composition of claim 15 further comprising activators one selected from the group comprising zinc oxide, stearic acid, silanes, and combinations thereof.

20. The carrier elastomeric composition of claim 15 further comprising one selected from the group comprising:

inorganic fillers, anti-oxidants, activators, processing aids and combinations thereof.

21. The carrier elastomeric composition of claim 15 wherein said pyrolyzed polymeric materials are derived from the pyrolysis of scrapped tires.

22. The carrier elastomeric composition of claim 15 wherein said fine agglomerates mixture of filler includes agglomerates having an average particle size of less than or equal to 35 nm.

23. The carrier elastomeric composition of claim 15 wherein said fine agglomerates mixture has a nitrogen surface area greater than or equal to 46 m2/g.

24. The carrier elastomeric composition of claim 15 wherein said fine agglomerates mixture has a nitrogen surface area greater than or equal to 53 mgl2/g.

25. The carrier elastomeric composition of claim 15 wherein said reclaimed carbonaceous material further comprises an inorganic functional filler in a range between about 5% to about 20% weight of said fine agglomerates mixture; and agglomerates having an average particle size less than or equal to 35 nm.

26. The carrier elastomeric composition of claim 15 further comprising an accelerator.

27. The carrier elastomeric composition of claim 15 further comprising a processing aid that includes one selected from the group comprising zinc soaps, fatty acid salts and combinations thereof.

28. The carrier elastomeric composition of claim 15 wherein said fine agglomerates mixture of filler includes agglomerates having an average particle size from about 10 microns to about 20 microns.

29. An carrier elastomeric composition comprising:

an elastomer material forming 20% by weight of said carrier elastomeric composition; a fine agglomerates mixture of filler derived from pylorized polymeric materials forming about 55% by weight of said carrier elastomeric composition; and
a processor oil forming about 25% by weight of said carrier elastomeric composition.

30. The carrier elastomeric composition of claim 29 wherein the elastomer material is one selected from the group comprising:

styrene butadiene copolymer, ethylene propylene diene M-class rubber, nitrile elastomers, butyl elastomers, natural rubber and combinations thereof.

31. The carrier elastomeric composition of claim 29 further comprising other filler materials one selected from the group comprising:

whiting, calcium carbonate, silica, kaolin, carbonates, barites and combinations thereof.

32. The carrier elastomeric composition of claim 29 further comprising anti-oxidants one selected from the group comprising phenyl amines, styrenated phenols, and combinations thereof.

33. The carrier elastomeric composition of claim 29 further comprising activators one selected from the group comprising zinc oxide, stearic acid, silanes, and combinations thereof.

34. The carrier elastomeric composition of claim 29 further comprising one selected from the group comprising:

inorganic fillers, anti-oxidants, activators, processing aids and combinations thereof.

35. The carrier elastomeric composition of claim 29 wherein said pyrolyzed polymeric materials are derived from the pyrolysis of scrapped tires.

36. The carrier elastomeric composition of claim 29 wherein said fine agglomerates mixture of filler includes agglomerates having an average particle size of less than or equal to 35 nm.

37. The carrier elastomeric composition of claim 29 wherein said fine agglomerates mixture has a nitrogen surface area greater than or equal to 46 m2/g.

38. The carrier elastomeric composition of claim 29 wherein said fine agglomerates mixture has a nitrogen surface area greater than or equal to 53 mgl2/g.

39. The carrier elastomeric composition of claim 29 wherein said reclaimed carbonaceous material further comprises an inorganic functional filler in a range between about 5% to about 20% weight of said fine agglomerates mixture and agglomerates having an average particle size less than or equal to 35 nm.

40. The carrier elastomeric composition of claim 29 wherein said fine agglomerates mixture of filler includes agglomerates having an average particle size from about 10 microns to about 20 microns.

41. The carrier elastomeric composition of claim 29 further comprising an accelerator.

42. The carrier elastomeric composition of claim 29 further comprising a processing aid that includes one selected from the group comprising zinc soaps, fatty acid salts and combinations thereof.

Patent History
Publication number: 20100292383
Type: Application
Filed: Oct 9, 2008
Publication Date: Nov 18, 2010
Applicant: CBp Carbon Industries, Inc. (New York, NY)
Inventor: John H. Fader (West Bloomfield, MI)
Application Number: 12/734,069
Classifications
Current U.S. Class: Sulfate Group, E.g., Calcium Sulfate, Etc. (524/423); Solid Polymer Derived From At Least One Diene Monomer (524/426); Kaolin Or Bentonite (524/447); Interpolymer With At Least One Aliphatic Hydrocarbon Monomer (524/578); From Hydrocarbon Monomer (524/570)
International Classification: C08K 3/30 (20060101); C08K 3/26 (20060101); C08K 3/34 (20060101); C08L 25/08 (20060101); C08L 23/00 (20060101);