DE2230762A1 - HIGH MODULE SOOT AND METHOD FOR PRODUCING IT - Google Patents

Description

The invention relates to carbon black with a high modulus in which a substantial proportion of the original structure is based a lower level as measured by the dibutyl phthalate test (DBP) and that compared in a vulcanized rubber compound has a significantly larger modulus than another highly structured carbon black, the a) measured according to the DBP test has an at least equivalent structure, but b). a combination of properties that would otherwise be based on rubber compounds with equivalent until greater reinforcement can be closed. Compared to the raw material from which the carbon black is made, this shows a substantially equivalent module

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with a significantly lower degree of structure measured according to the DBP test »The types of carbon black disclosed here can a tread rubber is also substantially the same as to give greater shelf life, and when pelletized they have significantly higher bulk density values than pellets made from the same carbon black with a higher percentage of uniform structure. The types of soot of the invention can be produced by stirring a moistened soot mass with a work performance that over the Work output that is necessary for the formation of wet pellets, but the rather fragile phases of the soot structure breaks out without significantly influencing the more permanent phases, which are primarily responsible are for developing a high modulus in a rubber compound.

Structure has previously been defined in connection with carbon black as a bond of carbon particles to form reticulated chains or lumps, which to some extent persist in a rubber compound even after vigorous mixing. So far, one believed - if everyone remained the same other factors - that the one developed in a rubber compound Module reflect the degree of structure of a certain type of carbon black, i.e. raising the structure increases the modulus of a rubber compound and vice versa. As can be seen, for example, from US Patents 3,010,794 and 3,010,795, the Control the modulus of a rubber containing carbon black by modifying the carbon black structure by adding an alkali metal to the carbon black formation zone reduced·. On the other hand, it is shown in US Pat. No. 2,985 that the module can be increased by raising the Soot structure by adding a normally gaseous paraffinic hydrocarbon to the area of the soot formation

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zone introduces in the pyrolysis of a liquid starting hydrocarbon begins. Various other US patents not listed here also describe methods for Raising or lowering of the carbon black structure in each case for the purpose of increasing or increasing the module of a rubber compound reduce.

Generally speaking, high modulus carbon blacks are oil furnace blacks, not thermal or gas blacks, with a structure characterized by an absorption value of at least about 100 cm / 100 g as measured by the dibutyl phthalate absorption test (ASTM-D2414, hereinafter simply "DBP ¹ '" Such carbon blacks with a high modulus generally have

3
a DBP value of 100 to 150 cm / g or more.

Designed to reinforce rubber tire treads Carbon blacks generally have a surface area

in the range from approx. 80 to approx. 180 m / g according to the electron microscope (EM) definitely. (The surface area is calculated from the arithmetic mean diameter of the Carbon black as determined by photomicrograph) · Lately the use of tread blacks has been with rather high than low structure widespread. There are a plethora of reasons for using such carbon blacks in Tire treads, among other things, the carbon black can be more easily introduced into the rubber and distributed in it Compound extrudes better, and there are signs too for high modulus tread material containing a high structure tread carbon black can expect a longer service life of the tread.

A very serious problem facing the manufacturer and supplier of soot, the relatively low bulk density measured according to the bulk density test (ASTM D1513-6O) is of High modulus carbon blacks and especially the tread grades that are sold in huge quantities. Soot types of high structure

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cannot be economically transferred from supplier to buyer transport if their bulk density is not increased sufficiently. Pelletizing processes are used to increase the soot density applied, and great care has always been taken to not to put undue work into the carbon black in these processes to degrade and consequently a module reduction and reduced durability of a tire-tread connection in which the soot is introduced to avoid »As a result, it was very difficult to pelletize To produce carbon black with a high modulus and an acceptable density, as it was known, on the one hand, that for the increase the density a greater amount of work was necessary and you on the other hand, feared that this necessarily greater amount of work would reduce the structure to one point would be seriously reduced in the modulus and durability of the rubber compound and so adversely affected would. Since the customer places special value on module and durability and not so much on bulk density, the carbon black manufacturer has chosen Restraint imposed on sacrificing structure to achieve higher density. Understandably however, there has been a need to produce higher density and structure carbon blacks with no modulus or durability (Abrasion resistance) to sacrifice.

It is therefore an object of the invention to provide a high modulus carbon black which largely reduces its original structure but which gives a rubber compound an essentially equal to higher modulus.

Another object of the invention is to provide a high-structure carbon black which largely reduces its original structure but that of a rubber tread compound is essentially the same or higher in modulus and abrasion resistance confers.

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Yet another object of the invention is to provide carbon black pellets of high structure which are characterized by high Bulk density without significant loss of modulus and / or tread durability.

Further "objects and advantages of the invention will become apparent from the following description in conjunction with the claims.

According to the invention, the objects mentioned can be achieved and the difficulties set out above can be overcome by a) a carbon black is produced which has a high modulus and a desired surface area (EM) in the end product, but b) an intentionally large excess of structure and c) a substantial part but not almost all of it Mechanically reduced structure of soot. However, the type and amount of work used to reduce the structure is such that neither the particle size nor the EM surface area nor does the volatile content significantly affect the influence of these properties on performance the rubber compound into which the carbon black is incorporated.

In the case of the highly structured carbon blacks of the invention, therefore, is an essential one Part of the original structure, measured by the DBP test, reduced, but when compared in a specifically mixed and cured vulcanized rubber compound, they have a significantly larger modulus than any other highly structured carbon black that a) after the DBP test has an at least equivalent structure but b) a combination of properties that would otherwise be equivalent to until greater reinforcement of the rubber compound occurs. Compared to the same soot, but with part of its structure long is not reduced so much to a lesser degree · can the types of carbon blacks disclosed have an essentially equivalent one

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Have modulus in the rubber compound, and when used as reinforcement carbon in a tire-tread compound find, they may have substantially equivalent to greater tread durability than any of those previously mentioned Give comparison carbon black.

The carbon blacks according to the invention in pelletized form are identified by a considerably higher bulk density than pellets made from the same carbon black, a larger one of which Part is in its original structure.

The highly desirable goal of a highly structured Carbon black with sufficient density and module developability and / or assured tread durability will be so achieved by the invention.

Contrary to earlier views, soot does not consist of separate, more or less round particles that are combined in an aggregate or a structural unit in the form of a lump or a branched chain. The paracrystalline structure in the particles with "randomly oriented graphite crystallites" is also not, as previously assumed, associated with little or no cohesion between the particles due to the planar layers of the crystallites. Burgess, Scott and Hess have shown using an electron microscope with high resolution and described in their study " Vulcanizate Performance as a Function of Carbon Black Morphology " presented to the Rubber Division of the American Chemical Society in October 1970) that in the so-called "aggregate" the so-called "particles" are not just attached to each other but are joined to a whole by a network of graphitic layers, which extends from one "particle" to the next and again to the next, etc., so that

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the aggregate actually does not consist of individual, separately formed particles, but rather a uniform one Structure that lacks a clear special plan and was given the name "paracrystalline graphitic unit" · According to these authors, these integrated units appear to have a main stem from which numerous Extend tubers that were previously perceived as the "particles" and which the authors now have "areas around them" Orientation of the graphitic layers ". In other words, the already mentioned graphitic layers in the Bulbs or areas look like spirals in two dimensions, like a fingerprint, and the planes, those closer to the surface extend and extend from the lower part of the area in each direction through the trunk of the unit to the next area, etc. The graphite layers are indeed bent and distorted, give but still the appearance of continuity in oneness rather than being confined to domains. Structure and therefore Module is such a function of the length or the form factor of the integrated paracrystalline graphite unit and not so much the type and degree of "particle aggregation".

The type and degree of soot structure reduction is important to achieving the objectives of the invention. The claimed For example, carbon blacks cannot be resolved using those described in U.S. Patents 2,066,274 and 3,024,092 Ball mill process or using the abrasive drum process described in US Pat. No. 2,890 * The mechanical Effect of such procedures leads to such a serious and excessive disintegration of the paracrystallines graphitic units that not only reduce the uniform structure but also the modulus of the carbon black will. In addition, these heavily ground soot react in such a way

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Measure with oxygen that the content of volatile substances (ASTM D 1620-60) is significantly increased. It should be emphasized that Carbon blacks made in accordance with conventional modulus reduction methods are intended for other purposes are than the carbon blacks produced according to the invention, i.e. the conventional methods are used to reduce modulus rather than increase or maintain modulus. They also cared Ball milled or abrasive drum treated carbon blacks in a highly saturated elastomer such as butyl rubber for greater reactivity to develop a carbon to rubber bond; but typically they disperse poor in unsaturated rubbers and difficult to process in them and deteriorate their tread durability.

According to the invention, however, the carbon black is changed in such a way that the modulus of the rubber compound is increased or essentially retained if the structure is also measured according to the DBP-i test is decreased, and if the modulus is decreased then no more than about 15, preferably 10% or less, which is determined by testing the strength of a cured sample under ordinary conditions and measuring the Modulus at 300% elongation.

Therefore, in the process of the present invention, the carbon black becomes one less subjected to severe mechanical treatment. The disclosed products have been successfully made according to general known processes for wet pelletizing carbon black, with one major and all important difference. In this procedure Considerably more work is expended on the moister soot powder mass during the movement for complete pelletization than was previously thought necessary for this purpose. For example, the method generally described and use the device of U.S. Patent 3,535,412, but

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you have to work with a much longer residence time for the moistened soot in the pelletizing zone. Otherwise or in connection with a longer treatment time, a higher stirring speed can be used than mentioned above Patent to carry out the process is prescribed, i.e. the top speed of the agitators can be significant more than 762 meters per minute (2500 feet), for example tip speeds in the range of approx. 25 to approx. 36 m per second (approx. 80 to approx. 120 feet) can be used with advantage.

However, the invention is of course not to be specific Device type for reducing the structure of soot is limited. Any suitable method and any suitable Use apparatus as long as the amount and type of energy available to modify the soot is satisfactory to to produce the desired properties defined here another procedure that is suitable for. can use this purpose is, for example, that in the US application Ser. No. 880 017 of November 26, 1969 described method by the same applicant, but it is then a sufficient work performance necessary to significantly reduce the structure of the soot. In any case, it should be the appropriate amount of work and mode for carrying out the invention can be selected such that 1) a substantial reduction in the soot structure is measured according to the DBP test, preferably to an extent of at least about 20%, but 2) the abrasion resistance a tread connection is either increased, remains essentially the same or is only slightly reduced. Another one An indication that the correct amount of labor was used to produce the disclosed carbon blacks is 1) an increase the EM surface area of no more than about 10%, preferably less and2) an insignificant or only

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low oxygen uptake to the extent that the content of volatile substances in the product does not exceed approx. 3 percent by weight. Those skilled in the art will therefore recognize that the The atmosphere and the temperature to which the soot is exposed during and after the structure reduction must be selected in this way should ensure that the uptake of excess oxygen is excluded in order to adversely affect the curing time and to avoid aging properties of the rubber compound.

In accordance with the invention, the paracrystalline graphitic units of the carbon black do not appear to be shattered to a substantial extent. It has been observed that these units, on the other hand, are worn all around without the ratio of width to length changing significantly. It has therefore been found that the reinforcing properties of a high modulus carbon black can be reduced by reducing the unit size can be improved, as measured by the average width or unit projected area, and that thereby the loss of gain, which is due to the reduction in the average unit length is compensated for. Such Parameters can be measured according to the methods described by Burgess, Scott and Hess in the paper mentioned.

The invention, in its broadest sense, is not directed to the use of any particular type of high modulus carbon black as a starting material limited. In the preferred range, however, for example for the reinforcement of tire treads, the carbon black should initially a DBP test value in the range of approx. 120 to approx. 200cm / 100g and an EM surface area in the range of

2
about 80 to 180m / g. As already stated, the structure of the soot, measured according to DBP, should be at least approx. 20%

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can be reduced, and can preferably be reduced by approx. 20 to approx. 40% reduced. Reduction of the structure by significantly more than approx. 40% causes an undesirable reduction in the Module and intake of excessive amounts of oxygen. Because the volatile content in the modified soot is not should be more than about 3 percent by weight, the starting material should therefore contain volatile substances which does not exceed approx. 3 percent by weight.

One of the particular advantages of the invention is that the carbon black with a reduced structure is a significantly larger one Has bulk density than the same carbon black in which a greater percentage of the structure is retained, for example, can the density be 150% or more higher and an effective value of 0.46 g / cm (26 pounds per cubic foot) or more to have.

It will be noted that the structure of the carbon black according to the invention can be reduced without prior, simultaneous or subsequent pelletization of the soot. On the other hand, the structure of the carbon black before or after a pelletizing step in the manufacturing process can be reduced ^ the soot can, for example, initially require relatively little work pelletized and then a greater amount of work applied which substantially reduces structure or the other way around. A preferably moistened mass can be used to reduce the structure or pelletize the carbon black Soot powder are exposed to fast-moving agitators that vigorously move the powder particles around in the mass and fling. It is therefore clear that the method can be carried out extremely conveniently if one has the desired Structure reduction and pelletization of the soot at the same time and in the same place by the same work. If one for simultaneous structure reduction and skin

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If a wet pelletizing process is used, the carbon black should be mixed in a cheek with a pelletizing liquid that is suitable for the formation of paste-like aggregates of the carbon black particles. Water or aqueous binder solutions. are normally used as wet pelletizers in amounts of about 65/35 to about 35/65 parts by weight of liquid to carbon black. It is common practice to dry pellets made with an aqueous pelletizing agent to remove virtually all moisture from the soot while maintaining conditions which preclude substantial addition of oxygen or other undesirable volatiles.

As already mentioned, the invention is favorably supplemented by generally known wet pelletizing processes in which a moistened mass of carbon black powder is moved axially through a long path and is subjected to a large number of blows caused by agitators that move transversely to the forward movement of the powder mass. Preferably the stirrers are elongated and extend from a rotatable shaft to the outside, extending axially with respect to the elongate path followed by the wetted mass ^v o ⁿ carbon black particles by the Pelletisierzone, wherein the agitator rotates at a speed such that the top speed is about 25 m per second. In many cases, a reasonable tip speed for these agitators will be in the range of about 25m to about 37m (80 to 120 feet) per second or more. The essential speed, however, depends, among other things, on the residence time of the carbon black in the pelletizing zone and on the degree to which the structure is to be reduced.

In view of the present teaching, it appears that carbon blacks produced by well-known processes have high Structure and high modulus through two structural phases

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are characterized by: 1) by a structure that is relatively stable and is resistant to breakdown unless subjected to hard knocks or pressure (as is the case with use a ball mill or attrition rollers) and 2) a structure that is more fragile and easier through less violent handling, such as lighter bumps and / or violent ones Rubbing together of the particles or the like can be reduced. Careful form factor analysis of the disclosed products shows that the paracrystalline graphite units on the whole are not divided into significantly smaller oxygen-reactive parts are shattered. Instead, it seems that they have only been sanded off somewhat in width and length to an extent that is practical or not particularly detrimental to the module, but not to such an extent that the EM surface area and the oxygen content of the soot can be changed significantly.

The invention will now be explained in more detail by means of examples, but it must be said that the invention is not based on the process conditions described here or generated thereby Products is limited.

EXAMPLE 1

High modulus furnace blacks, HV-820, HV-830, and HV-840 were made substantially in accordance with that disclosed in U.S. Patent 3,490,869 described method produced. From Table I it can be seen that these carbon blacks were essentially pelletized before they were pelletized had the same colloidal properties except for their DBP values. The fineness and thus also the EM surface area this carbon black was purposely kept the same in all three manufacturing processes, but the DBP was kept through Adjustment of the process conditions changed for each method to achieve different DBP target values. Hence all of them had three carbon blacks have the same surface area before they are pelletized

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ρ
expansion (EM) of 104m / g, but DBP values of 175 in each case,

or 132cm ³ / 100g.

Each of these carbon blacks was then wet pelletized using the apparatus and apparatus described in U.S. Patent 3,535,412 method described therein, and in particular using the apparatus used in Experiment 2 of this patent and of the method, with such a JR stirrer shaft speed in each case was used so that the agitators had a top speed of approx. 12.8 m per second (762 m per minute) achieved. The resulting wet pellets were then dried to a moisture level of about 1.5 percent by weight or less dried. The dried wet pellets produced in this way are designated as HV-82OA, HV-83OA and HV-840A.

The HV-82O and HV-830 carbon blacks were also made after the aforesaid patented process and the patented device wet pelletized, but different methods than the previous experiments in that the pelletizer was used was slightly smaller (0.20 m diameter χ 0.63 m length), a higher stirring speed was used and each carbon black was used twice was sent through the pelletizer. The top speed of the agitators was during the first and second pass of HV-820 respectively 26m and 31m per second (85f.p.s. and 103 f.p.s.) and during the first and second pass of HV-830 respectively 20m and 26m per second (65 and 85 f.p.s.). The aim of such a pelletization the carbon black was initially to change the structure measured according to DBP and so the bulk density of the pellets on the Bringing grade of HV-840A carbon blacks. (As a result, HV-840 was not used in this pelletizer at a high level of work either pelletized because this means that the DBP and the module des

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CD CD OO

Soot properties

Surface area (EM), m? / G DBP, cm3 / 100g (ASTM D2414) Iodine Ads. No. (ASTM D 1510-65) Transmission,% (ASTM D 1618-65T) Volatile matter content,% by weight (ASTM D 1620-60)

Pellet bulk density, (ASTM D 1513-60) g / cm (lb./cu.ft.)

Stress-strain properties, hardened at 145OC

60 'module, 300% kg / cm ² (psi)

60 ', tensile strength kg / cm (psi)

60 'elongation at break,%

60 'Shore hardness

100 'tensile strength kg / cm (psi;

Log IR

Dispersion, visible rebound, 100 'Goodrich HBU, 100'

Table 1 HV-82OB- —HV-830 HV-83OA HV-83OB HV-840 HV-BVlC / HV-BPO HV-S2OA 104 104 104 104 * 104 104 104 104 124 154 140 126 132 123 175 158 91 96 ^ 92 87 103 94 104 94 82 65 71 80 73 78 72 79

1.6

1.3

130, 2 116.9 (1845) (1670) 206.1 204.5 (2930) (2945) 450 490 58 58 212.4 214.5 (3020) (3050) 3.9 4.0 4.0 4.0 56.4 55.9 85 87

1.0

1.3

283 O, 365 O, 307 O, 346 (17, 7) (22, 8th) (19, 2) (21, 6)

127- (1800)
218.3
(3105)
480
58

213.8

(3040)

3.8

3.9

56.4

86

106.8
: i525)
208.9
: 297O)
530
58

208.2

2960)

3.8

4.0

54.4

87

1.0

0.347 (21.6)

100.2 (1425) 213.4 (3035) 545 55

216.6 (3080) 3.6 4.0 55.4 85 K)

CD

<J5 ISJ

Table 1 (continued )

HV-820 HV 82OA HV 82OB - HV-830 HV 83OA HV 83OB -HV-840 HV 84OJ

Actual road abrasion resistance based on HV-84O B

Center line,%

Slow 107 104 101 100

Fast 101 105 103 100

Total,% . *

»O Slowly 100 98 98 97

° Fast 104 104 104 101

CD OO CO ΓΟ

2 ^ ι

Λ *

Soot would have been reduced and at the same time its density would have been increased to a level different from the target product HV-84OA). The wet pellets obtained were then dried to a moisture level of about 1.5 weight percent or less and named HV-820 and HV-83OB.

Each of the dried wet pelletized carbon blacks was then converted into a tire-tread rubber compound is introduced, while proceeding according to a standardized mixing process and using the recipe listed below:

Recipe Component parts by weight

SBR-1712 (50 parts polymer, 18.75 parts oil) 96

Cis polybutadiene '30

Soot 70

Circosol 42 χ H (process oil) 14

Zinc oxide "4.0

Stearic acid 2.0

Thermoflex A (antioxidant) 1.5

NOBS Special (hardener) 1,2

Sulfur 1.8

Each of the obtained compounds was then cured under the same conditions. The stress properties, which according to Standard ASTM methods determined for the cured compounds are shown in Table I. Also shown is tread durability of connections, according to existing road tests of automobile tires under carefully controlled and uniform conditions at high and low speeds was determined.

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The HV-83OB carbon black made according to the invention with a approx. 20% reduced HV-830-DBP value had such surface expansion (EM), DBP, iodine absorption and transmission values, that one skilled in the art must conclude that the reinforcement of the rubber compound is equivalent to that of HV-84OA. The HV-83OB soot however, had a significantly higher modulus and almost equivalent road abrasion resistance. Besides, they had HV-83OB pellets have virtually the same bulk density as HV-840A.

In particular, it should be the HV-82OB carbon black produced according to the invention with an HV-820-DBP value reduced by about 30% More attention should be paid to the surface area, (EM) DBP, iodine absorption and transmission values from which one skilled in the art can conclude that the reinforcement of the rubber compound is equivalent to that of HV-840A. However, the HV-82OB carbon black had a much larger modulus and significantly higher road abrasion resistance and at the same time a higher bulk density than HV-840A.

Therefore, HV-82OB and HV-840A made in accordance with conventional practice based on a comparison of colloidal properties with respect to rubber reinforcement properties and abrasion resistance, yet HV-82OB is unexpected and amazing superior to the HV-840A in this regard. In addition, the higher density of 0.018g / cm (1 Ib percu.ft.) With HV-82OB should not go unnoticed, because even such an apparently small increase means a considerable saving in shipping costs.

It is certainly recognized that the higher energy required to produce HV-82OB is compared with its higher value HV-840A is more than made up for. Without the advantage of

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With the invention, however, those skilled in the art would certainly have opted for the older method of manufacturing the highest module The highest density of the pellets was decided, that is, by producing a carbon black with a structure indicated by DBP to achieve the best modulus and the best density in each case at the highest level and through subsequent pelletizing in a manner that substantially maintains the DBP, such as the HV-82OA, HV-83OA, and HV-84OA. Continue on this One more point, it should be said that it has long been known that increasing the DBP value of the carbon black is a reduction the density of the pellets that are formed during the pelletization at a certain work stage and that although the density is increased by a moderate increase in the labor input, this is accompanied by a loss of module. What what was not known was that by first increasing the DBP of the carbon black sharply and then increasing the work of pelletizing to an insignificantly larger amount, i.e. one which is expected to be detrimental to modulus and wear has the effect that the density can be greatly increased without resulting in greater damage to the module and / or abrasion. Viewed differently, the present carbon black can have a considerably higher modulus than another pelletized carbon black with an originally lower DBP than that from which the present carbon blacks are derived, but the comparison can. also show that the present carbon blacks nevertheless have no more than approximately the same DBP value while their other properties suggest equivalent or even less equivalent reinforcement of the rubber compound.

EXAMPLE 2

HV-820 carbon black according to Example 1 was made according to those described for HV * 82OB The process was pelletized again, but different amounts of work were used in accordance with the invention to obtain the measurable

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Decrease structure. Three pelletizing attempts were made, and in each case the top speed of the agitators was 26 meters per second (85 f.p.s.) but the soot would passed through the pelletizer different times during the various experiments, i.e. there were 3.5 and 8 passes. The resulting wet pellets were then adjusted to a moisture content dried below about 1.5 percent by weight and were named HV-820C, HV-82OD and HV-82OE, respectively.

The dried pellets produced in this example, some of the HV-82OA pellets according to Example 1 and also conventional Pellets made from a high quality HAF-HM carbon black and an ISAF carbon black were made into a tire-tread rubber compound according to the recipe and the mixing and hardening processes introduced according to Example 1. Colloidal properties of carbon blacks and stress-strain properties of the cured compounds determined by the same ASTM methods as in Example 1, are shown in Table II. Tread wear, determined according to the methods described in Example 1, is also shown in Table II.

From Table II it can be determined that the DBP measured structure of HV-820 in the manufacture of HV-82OC, HV-82OD and HV-82OE was decreased by approximately 26%, 31% and 35%, respectively. It can also be seen that the density of the pellets was compared to HV-82OA was respectively increased by approx. 131%, 137% and 150% and in each case was considerably higher than with the commercially available HAF-HM and ISAF pellets. However, although the Pellets from HV-82OE have an astonishingly high density of practically 0.432 g / cm (27 Ib. Cu. Ft.) Or 150% higher Density than HV-82OA, the module was essentially the same, i.e. the module of HV-82OE made up more than 90% of the module of HV-82OC off. It was also surprising that the tread abrasion resistance of HV-82OE was substantially equal to or better than that of HV-82OA.

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Tabel

Ru. "> Ci gens chef ten

HV-S20A HV-82OC HV-82OD HV-82OE conventional 3 passages 5 passages 8 passages passages

Surface finish p • elongation., (EK), m / g DEP, cm / ΙΟΟα (ASTK D 2414) "JodAcs. No. (ASTK D 1510-65) transmission,% (ASTK D 1618-65T) Volatile matter content, weight / (ASTK D 1620-60)

Pellet bulk density D 1513-60)

104 - 158 129 94 91 79 89

1.1

2.0

0.283 0.371 .g / cm x ³ (lbs./cu.ft.) (17.7) (23.2)

Stress-strain properties, hardened at 145OC

60 'module,
kg / crn (psi

300%,

149.7 2125)

146.2 2075)

60 'tensile strength kg / cm ² (psi)

60 'Elongation at break,% 60' Shore hardness 100 'Tensile strength, kg / cm ² (psi) Log IR
Dispersion, visible
Rebound, 100 Goodrich HBU, 100 '

211.8 223.3 3155) (3175) 420 59

4.2

4.3

4th , 0 4th , 0 57 , 4 57 , 4 80 84

121 91 88

1.9

105.6 113

91

89

HAF-HM
conventional
lich IS ^ F
conventional
borrowed 110 118 125 110 95 120 83 97

1.2

137.5 (1950)

135.7 1925)

223.3 225.8

(3175) (3210)

455 59

.4.4

4.0 57.4

84

4.3

4.0 57.9

76 123.5
.1750)

218
! 3100)
480
58

3.4

4.0
55.4

83

0.98

O, 387 ( O, 426 ( O, 342 ( O, 350 (24, 2) 26, 6) 21 4) 21 9)

103.7 1475)

235.6 3350) 545 59

2.4

4.0 52.0

85

Russian shops HV-82OA conventional lich LOG IK 4.2 Dispersion, visible 4.0 Rebound, 100 ' 57.4 Goodrich HAY, 100 ' 80 Actual Road abrasion strength zoaen on HV-82OA Center line,% Slow 100 Fast 100 Total,% Slow 100 Fast 100

Table 2 (continuation)

HV-8 2OC 3 passes

4.3

4.0 57.4 84

101 92

102 94

HV-82OD HV-82OE HAF-HFi I SAT ¹ 5 through 8 through conventional here corridors corridors lich convenient 4.4 4.3 3.4 2.4 4.0 4.0 4.0 4.0 57.4 57.9 55.4 5?, 0 .84 76 83 55

104 96

106 98

98 90

100 92

103 91

108 93

CD (Ji

JLj

Where the tread abrasion resistance is not such a critical factor And the 'module is more important, pellets can be higher density as HV-82OC and HV-82OD.

It should not be overlooked how significant it is that the HV-82OC, HV-82OD and HV ¹ 82OE pellets not only had a higher density but also a much larger modulus and better tread abrasion resistance than the HAF HM carbon black. This is extremely astonishing in view of the fact that the HAF-HM carbon black had a somewhat finer particle size and also an equivalent to higher structure and therefore one would have to assume that it would have a higher modulus and greater abrasion resistance than the HV-82OC-bis HV-82OE carbon blacks.

A similar, more impressive comparison can be made between HV-82OE and ISAF, a widely used tread black that provides a tire tread with the highest levels of reinforcement and abrasion resistance. Although the DBP values of these two types of carbon black are approximately the same, HV-83OE had a much higher modulus and at least equivalent tread abrasion resistance, and it is particularly important that the HV-82OE pellets have a 0.072g / cm ³ (4.5 .lbs. per cubic foot) or a density 121% higher.

Since the shipping costs largely depend on the space required for transport, you probably know better appreciate that the density of high structure carbon blacks greatly increases can be achieved while at the same time achieving the other objects of the invention. Since the customer is buying by weight, a could Supplier for example send HV-82OE and then needed only about two-thirds of the shipping volume that would have been required for the HV-82OA, making it a huge savings Effect shipping costs.

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It has now been found that even more work has been done on pellerization of carbon blacks with high structure can be used sis was used on HV-82OE to allow for even larger increases in density, e.g. to effect more than 432g / cm (27 lbs. per cubic foot), and even if the module waste is a bit larger, it can go through tread abrasion resistance imparted to carbon black on a rubber tire tread remain essentially unaffected and even be improved. So if there is a significant loss of modules in Can be purchased, the density of a high modulus carbon black can be greatly increased without significantly reducing the road wear to adversely affect by the structure of the carbon black to an even greater extent than previously indicated by the present process reduced.

The pellet density of a high modulus tread black became

3
for example increased from 273 to 46 kg / m (17.1 to 26 lbs. p. cu. ft.), and although the modulus was reduced by 20%, the tread abrasion resistance was increased by 4%. In another case, the pellet density of a high modulus tread ^{black was increased from 37 kg / m 3} to 44 kg / m ³ (19.8 to 27.5 lbs. Cu.ft.) and the road wear remained unaffected, although the modulus fell by 18%.

In any event, therefore, high density pellets can be made from a high modulus carbon black according to the present method in which part of the original soot structure measured according to DBP is reduced, and the pellets obtained are a substantial one have a higher bulk density than other pellets made from the same carbon black, but in which a higher proportion of measured structure is obtained.

Using the present carbon blacks has been found to have the further advantage that these carbon blacks are more rapidly converted into a rubber compound can be introduced. For example, it was found that HV-82OE according to Example 2 was uniformly incorporated into the rubber in only 75% of the time required for the HV-820A could be mixed in.

209882 / 10G0

Claims (33)

Expectations High modulus carbon black that has a substantial portion of the original structure on a dibutyl phthalate absorption test (DBP) measured lower degree, characterized in that it is compared to a vulcanized Rubber compound has a much higher modulus. than another soot of high structure, the one a) at least equivalent structure measured according to the DBP test and b) has a combination of properties which one otherwise encountered with equivalent to larger reinforcements of the rubber compound. 2. Soot of reduced structure with high modulus according to claim 1, characterized by a DBP test value in the range of approx. 100 to approx. 180cm / 100g and a surface area (EM) 2
in the range from approx. 80 to approx. 180 m / g. 3. Carbon black according to claim 1 or 2, characterized by a volatile content of not more than about 3 percent by weight. 4. High-modulus carbon black of reduced structure according to one of the claims 1 to 3, characterized in that it is in the form of dried pellets which have a bulk density that is significant is greater than that of dried pellets made from the same carbon black with a greater proportion of structure. 5. High-modulus carbon black of reduced structure according to one of the preceding Claims, characterized by an essentially equal to only slightly higher surface area (EM) than that the same soot, in which a significantly higher proportion of the structure has remained. 209882/1 060 6. High-modulus carbon black of reduced structure according to one of the preceding Claims, characterized in that it is a rubber tread compound is able to impart a substantially equivalent to higher abrasion resistance than the comparison carbon black. 7. High-modulus carbon black of reduced structure according to one of the preceding Claims, characterized in that its structure measured according to the DBP test by approx. 20 to approx. 40% of the original Structure is reduced. 8. High-modulus carbon black, which is a substantial part of the original Structure to a lesser degree as measured by the dibutyl phthalate test (DBP) is reduced, in particular according to one of the preceding claims, characterized in that it is in of a vulcanized rubber compound has a substantially equivalent modulus as compared to the same carbon black in which part, but a much smaller part, of the original structure is reduced to a lesser degree. 9. High-modulus carbon black of reduced structure according to claim 8, characterized by a DBP test value in the range from approx. 100 to approx. 180cm / 100g and a surface area (EM) in the range ρ
from approx. 80 to approx. 180m / g. 10. Carbon black according to claim 8 or 9, characterized by a volatile content of no more than about three percent by weight. 11. High-modulus carbon black of reduced structure according to one of the claims 8 to 10, characterized in that it is in the form of dried pellets with a bulk density that is significant 209882/1060 is greater than the bulk density of dried pellets made from the same carbon black, in which a greater Structural portion. Is. Preserved. 12. Cooking module soot of reduced structure according to one of the claims 8 to 11, characterized in that it has essentially the same or only slightly larger surface area (EM) than the same carbon black in which a larger structural portion is retained. 13. High-modulus carbon black of reduced structure according to one of claims 8 to 12, characterized in that it is a rubber tread compound is able to impart a substantially equivalent to greater abrasion resistance than the comparison carbon black. 14. High-modulus carbon black of reduced structure according to one of the claims 8 to 13, characterized by a DBP test value in the range from approx. 100 to approx. 180 cm / 100 g and a surface area (EK) in the range from approx. 80 to approx. 180m / g. 15. A method for significantly increasing the bulk density of a highly structured carbon black without significant loss of the rubber module, characterized in that a powdery mass of the carbon black is subjected to a mechanical work which is in excess of the amount necessary to form wet carbon black pellets and which substantially affects the DBP test value of the carbon black reduced, without its surface area (EM) significantly to increase. 16. The method · according to claim 15, characterized in that a Soot is subjected to the treatment, which has a DBP test value in the range of approx. 120 to approx. 200 cm / 100 g and an upper 2 has flat expansion (EM) of approx. 80 to approx. 180m / g, and 209882/1060 A 14 210 - 2 ^ - its degree of structure, measured according to the DBP test, is reduced by approx. 20 to approx. 40% when the work is used. 17. The method according to claim 15 or 16, characterized in that the treatment is carried out so that the content "on
volatile substances in soot after applying the mechanical
Work does not exceed approx. 3 percent by weight. IS. Process according to one of Claims 15 to 17, characterized in that the carbon black of reduced structure obtained is wet pelletized and then dried for the production of dry pellets and the bulk density of the pellets according to their
Drying is greater than that of dried wet pellets, which are produced with an amount of mechanical work that is only sufficient for pelletizing the soot and is less able to reduce the measurable structure of the soot. 19. Process for increasing the bulk density of a carbon black and
Creation of a converted product from this with modular
and surface expansion values (EM) within predetermined limits, in particular according to one of claims 15 to 18, characterized in that a) produces a soot .with a surface area (EM) within the limits predetermined for the converted product, but with a significantly higher one measured according to the DBP test Structure as desired, and then you b) the measurable structure of the soot is substantially reduced, substantially but not its module, and by reducing the structure, the surface area (EM) of the soot is essentially is not changed. 209882/1060 4? Io - ^ - 7230762 20. The method according to claim 19, characterized in that the measurable structure of the soot is reduced by a ■ Mass of soot particles exposed to fast moving Subjected to mechanical devices that violently whirl around the soot particles in the mass. 21. The method according to claim 19 or 20, characterized in that the mass of the soot particles is mixed with a liquid in amounts which are suitable for forming paste-like
Aggregates of the particles and the moistened powder obtained is vigorously stirred and swirled back and forth. 22. The method according to claim 20 or 21, characterized in that the stirred and swirled back and forth soot is pelletized will. 23. The method according to claim 22, characterized in that the wet pellets obtained are dried and drying conditions are maintained which are essential
Exclude the addition of oxygen to the soot. 24. The method according to any one of claims 19 to 23, characterized
characterized in that the moistened mass of soot particles moves forward on an elongated path and is exposed to an abundance of impacts which
through transverse to the direction of the forward movement of the mass
moving agitators are caused .. 25. The method according to claim 24, characterized in that the stirring members are long and extend from a rotatable shaft 209 882/1060 A 14 210 tf extend outwards, which in relation to the elongated path on which the moistened mass moves forward, extends axially and the agitator members have an edge speed of at least about 24 m per second (80 ft.) while moving through the till. 26. The method according to claim 25, characterized in that the edge speed of the agitator members in the range of about 24 to is approximately 37 meters per second (80 to approximately 120 feet). 27. The method according to any one of claims 19 to 26, characterized in that the converted soot is pelletized before doing the work that reduces the structure of the soot. 28. The method according to claim 27, characterized in that the wet pellets of the converted soot under conditions produced, recovered and dried, which have a substantial addition of oxygen to the converted Exclude soot. 29.High-density pellets made from a high-modulus tread black, in which a substantial part of the original structure measured according to the dibutyl phthalate absorption test (DBP) is reduced, the pellets have a much higher bulk 209882/1060 A 14 210 y £ " denser than other pellets of the same carbon black with a higher measurable structural content, characterized that the carbon black of the higher density pellets of a rubber tread compound substantially at least equivalent road abrasion resistance compared to that gives more structured soot to the other pellets. 30. High density pellets according to claim 29, characterized in that that road abrasion resistance in a tire tread is measured in .der the rubber is a mixture of BR and OEP rubbers. 31. High modulus carbon black in which a substantial part of the original Structure, measured according to the dibutyl phthalate absorption test (DBP), is reduced, with a surface 2 expansion (EM) in the range from approx. 80 to approx. 180m / g, a DPB test value in the range of about 100 to about 180, and which is capable of a rubber tire tread compound substantially at least equivalent road abrasion resistance compared to the same carbon black lend, both of which have a higher percentage that is measurable Structure is preserved '.., 32. High-modulus carbon black with reduced structure according to claim 31 a volatile content of no more than about 3 percent by weight. 33. high-modulus carbon black of reduced structure according to claim 31 or 32, characterized in that road abrasion resistance is measured in a tire tread in which the rubber is a mixture of BR and OEP rubbers. 209882/1060