CA2121693A1 - Carbon blacks - Google Patents

Abstract

Novel carbon blacks that impart advantageous properties to rubber and plastic compositions and may be utilized in place of lamp blacks, thermal carbon blacks and blends of carbon blacks. Also disclosed are novel rubber and plastic compositions incorporating the novel carbon blacks which exhibit advantageous combinations of compound processing and physical performance properties.

Description

~O 94/05732 P~/US93/08129 CARBON BLACKS

This application is a continuation-in-part of United States Pa~ent Application Serial Number 07/935,794, Filed ~ugust 27, 1992.

s FIELD OF THE INVENTION
The present invention relates to new carbon blacks which are suitable for various applications and particularly well suited for use in plastic and rubber compositions.

BACKGROUND
Carbon blacks may be utilized as pigments, fillers, reinforcing agents, and for a variety of other applications.
They are widely used in the preparation of rubber compositions and plastic compositions where it is desirable to achieve an optimal combination of compound processing characteristi::s and physical properties of fabricated parts.
Carbon blacks are generally characterized on the basis of their properties including, but not limited to, their surface areas, surface chemistry, aggregate sizes, and - ~ particle sizes. The properties of car~on blacks are analytically determined ~y tests known to the art, including iodine~adsorptior~ number (I2No.), dibutyl phthalate adsorption (DBP), Tint vaIue (TINT~, Dst, Dmode -and M-Ratio that is -~ defined as the median Stokes diameter divided by the mode S~okes diameter (M-Ratio = Dst/Dmode).
From the prior art several references are known. These .
include U.S. Patent No. 4,366,139; U.S. Patent No. 4,~21,772;
U.S. Patent No. 3,79g,788; U.S. Patent No. 3,7~7,562; Soviet Union 1279g91; Canadian 455504; Japanese 61-047759; British 1022988; and Japanese 61-283635. None of the aforementioned 30 references disclose the carbon black products of the present invention. Moreover, none of the aforementioned references describe the use for which the carbon blacks of the present invention are intended.

W094/05732 2 1 2 1 6 9 3 - 2 - PCT/US93/081~

SUMMARY QF THE INVENTION
We have discovered nine new classes of carbon blacks advantageous for use in rubber and plas~ic compositions where ¦ compound processing and physical properties such as mixing energy, viscosity, cure rate, extrusion shrinkage, tensile, fatigue life, compression set, hardness, resistivity and surface appearance are important. Th~se carbon blacks have been found to provide unique combinations of properties that make them especially well suited for use in extrusion, molded part, hose and belt applications.
The first class of carbon blacks has an Iodine adsorption number (I2No.) of 17-23 mg/g (milligrams I2 per gram carbon black) and a DBP (dibutyl phthalate value) of 115-150 cc/lOOg ~: (cubic centimeters of dibutyl phthalate per 100 grams carbon black). Preferably this class of carbon blacks is characterized by having an I2No. of about 20 mg/g.
he second class of carbon blacks has an I~No. of 10-19 ~ mg/g and a DBP of 70-95 cctlOOg.
`~ The third class of carbon blacks has an I2No. of 12-20 mg/g and a DBP of 34-65 cc/lOOg. Preferably this class of carbon blacks is characterized by having an I2No. of 14-18 mg/g and a DBP of 36-55 cc/lOOg, and more preferably a DBP of ~-~ either 36-42 cc/lOOg or 45-55 cc/lOOg.
` The fourth class of carbon blacks has an I2No~ of 28-43 25~:- mg/q, and a DBP of 28-47 cc/lOOg. Preferably this class of carbon blacks is characterized by having an I2No. of 30-42mg/g.
The fifth class of carbon blacks has an I2No. of 8-32 mg/g, a DBP of 28-150 cc/lOOg and an M-Ratio of 1.25-2.00.
The 5ixth class of carbon blacks has an I2No. of 33-70 mg/g, a DBP of 28-60 cc/lOOg and an M-Ratio of 1.~5~2.00.
: The saventh class o~ carbon blacks has an I2No. of 42-50 mg/g, a DBP of 61-105 cc/lOOg and an M-Ratio of 1.25-2.00.
' The eighth class of carbon blacks has an I2No. of 51-62 mg/g, a DBP of 61-125 cc/lOOg and an M-Ratio of 1.25-2.00.
The ninth class of carbon blacks has an I2No. of 63-70 ~ , ~ .

~094/05732 2 1 2 1 6 9 ~ PC~/US93/08129 -3~

mg/g, a DBP of 61-105 cc/lOOg and an M-Ratio o~ 1.25-2.00.
~ e have also discovered new classes of rubber and plastic composi~ions containing the carbon blacks.
-The carbon blacks of the present invention may be S produced in a furnace carbon black reactor having a combustion zone, a transition zone, and a reaction zone. A carbon black yie~ding feedstock is injected into a hot combustion gas stream. The resultant mixture of hot combustion gases and feedstock passes into the reaction zone. Pyrolysis of the carbon black yielding feedstock is stopped by quenching the ~ mixture after the carbon blacks of the present invention have ;~ been formed. Preferably pyrolysis is stopped by injecting a quenching fluid. The process for preparing the novel carbon blacks of the present invention will be described in greater detail hereinafter.
The rubbers and plastics for which the novel carbon blacks of this invention are effectiv~ includa natural and ~;synthetic rubbers and plastics. Generally, amounts of the carbon black product ranging from about 10 to about 300 parts by weight can be used for each 100 paxts by weight of rubber or plastic.
Among the rubbers or plastics suitable for use with the present invention are natural rubber, synthetic rubber and their derivatives such as chlorinated rubber; copolymers of from about 10 to about 70 percent by weight of styrene and from about 90 to about 30 percent by weight of butadiene such as copolymer of 19 parts styrene and 81 parts butadiene, a ~`copolymer of 30 par~s styrene and 70 parts butadiene, a copolymer of 43 parts styrene and 57 parts butadiene and a copolymer of 50 parts styrene and 50 parts butadiene; polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, polychloroprene, and the like, and copolymers of such conjugated dienes with an ethylenic group-containing -~ -monomer copolymerizable therewith such as styrene, methyl s*yrene, chlorostyrene, acrylonitrile, 2-vinyl-pyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, alkyl-substituted acrylates, vinyl ketone, methyl isopropenyl ketone, methyl vinyl ether, W094/05732 2 1 2 1 6 9 3 _4_ PCT/US93/081~

alphamsthylene carboxylic acids and the esters and amides thereof such as acrylic acid and dialkylacrylic acid amide;
also suitable for use herein arP copolymers of ethylene and other high alpha olefins such as propylene, butene-1 and penetene-l; particularly preferred are the e~hylene-propylene copolymers wherein the ethylene content ranges from 20 to 90 percent by weight and also the ethylene-propylene polymars which additionally contain a third monomer such as dicyclopentadiene, 1,4 hexadiene and methylene norbornene.
Additionally preferred polymeric compositions are olefins such as polypropylene and polyethylene.
An advantage of the carbon blacks of the present invention is that the carbon blacks are useful for incorporation into natural rubbers, synthetic rubbers, plastics or blends thPreof for industrial applications, particularly where compound processing and part performance characteristics are important.
A further advantage of the carbon blacks of the present invention is that certain of the carbon ~lacks of the present invention will replace blends of carbon blacks in applications that currently require the use of blends of carbon blacks to achie~e desired performance characteristics.
Other advantages of the present invention will become apparent from the following more detailed description of the ,~ ~
~ 25 inven~ion.

i~
: -~ , ' .~094/0~732 PCT/US~3/08129 BRIEF DESCRIPTION OF THE DRAWINGS:
Figure 1 i5 a cross-sectional view of a portion of one type of furnace carbon black reactor which may be utilized to produce the carbon blacks of the present invention.
Figure 2 is a sample histogra~ of the weight fraction of the aggregates of a carbon black sample versus the Stokes Diameter in a given sample.

DETAILED DESCRIPTION OF THE INVENTION
The analytical properties of each of the nine classes of ~: 10 carbon blacks of the present invention are set forth in Tab~e 1 below:
: Table 1.
~:
_ _ Class I2 No. D3P Ratio ~ , _ _ ~1: First 17-23 115- ___ First 20 150 ___ Preferred 111550-~ ~ ~ _ ~1 Second 10-19 70-95 ___ . Third 12-20 34-65 ___ ~ Third 14-18 3 6-55 ___ 11~1 20 Preferred 14-18 36-42 ___ Third More 14-18 4S-55 ___ Preferred ~ Third.More ;~ Preferred 1~ 25 : Fourth 28-43 28-47 ___ Fourth 30-42 28-47 ___ Preferred . . I
Fifth 8-32 2B- 1.25-~; 150 2 . 00 S ixth 3 3 -7o 2 8-60 li.2050-~ l : 30 Seventh 42-50 61- 1.25-105 2.00 ~, I
Eighth 51-62 61- 1. 25-~- ~: I
Ninth 63-70 61- 1. 25-~ l 105 2.00 : -~: ' W094/05732 2 1 2 1 6 9 3 -6- PCT/US93/08 ~

The carbon blacks of the present invention may be produced in a modular, also referred to as "staged", furnace carbon black reactor. A section of a typical modular furnace carbon blac~ reactor which may be utilized to produce the carbon black of the present invention is depicted in Figure 1. Other details of a typical modular furnace carbon black reactor may be found, for example, in the description contained in U.S. Patent No~ 3,922,335, the disclosure of which is herein incorporated by reference. A carbon black reac~or particularly well-suited for the production of the carbon blacks of the present invention is described in commonly assigned U.S. patent application serial number 07/818,943, filed January 10, 1992, the disclosure of which is hereby incorporated by reference. The carbon blacks of the Examples described herein were made by the process described in the '943 application.
The '943 application describes a process for producing carbon blacks wherein auxiliary hydrocarbon is added to the reaction zone of a multistage reactor and the primary com~ustion and overall combustion of the reaction are adjusted so that the SSI of the process is less than zero. The SSI of the process may be determined by the following rela~ionships:
SSI = SASmf SASah ~1 wh~re (DBP)mf : ~ ~DBP) ah SAS = SAS
f ~ ( IodineNumber)mf ' ~ ~ (IodineNumbeI:
~2) SAS mf I = Absolute ~alue of SAS mf ;
~tDBP) mf - the change in DBPA of the carbon black due to a change in feedstock flow rate while all other process operating conditions are held constant;
, (Iodine Number) ~f = the change in iodine adsorption number of the carbon black due to a change in feedstock flow rate while all other process operating conditions are held constant;

/~5732 -7- PCT/US93/08129 ~(DBP~ ah - the change in DBPA of the carbon black due to a change in auxiliary hydro~arbon flow rate while all other process operating conditions are held constant; and ~Iodine Numbe~) ah the change in iodine adsorption number of the carbon black due to a change in auxiliary hydrocarbon flow rate while all other process operating conditions are held constant.

The "auxiliary hydrocarbon" comprises hydrogen or any hydrocarbon having a molar hydrogen-to-carbon ratio gr2ater than the molar hydrogen-to-carbon ratio of the feedstock.
lSReferring to Figure l, the carbon blacks of the present invention may be produced in a furnace carbon black reactor 2, having a combustion zone lO, which has a zone of converging iamPter 11, transition zone 12, entry section 18, and reaction zone l9. The diameter of the combustion zone l~, up to the point where the zone of converging diameter ll begins, is shown as D-l; the diameter of zone l~, as D-2; the ~:~ diameters of the stepped entry section, 18, as D-4, D-5, D-6, :; and D-7; and the diameter of zone l9, as D-3. The length of the combustion zone lO, up to the point where the zone of : 25 converging diameter ll begins, is shown as L-l; the length of the zone of converging diameter is shown as L-2; the length of the transition zone is shown as L-3; and the lengths of the steps in the reac~or entry section, 18, as L-4, L-5, L-6 and 7.
30To produce carbon blacks, hot combustion gases are g~nerated in combustion zone lO, by contacting a liquid or gaseous fuel with a suitable oxidant stream such as air, oxygen, mixtures of air and oxygen or th~ like. Among the fuels suitable ~or use in contacting the oxidant stream in combustion :~ 35 zon~ lO to generate the hot combustion gases are any of the : rea~ily combustible gas, vapor, or liquid streams such as natural gas, hydrogen, carbon monoxide, methane, acetylene, alcoho~, or ~erosene. It is generally preferred, however, to ~:utilize fuels having a high content of carbon-containing .

W094/05732 2 1 2 1 6 9 3 -8- P~T/US93/0~1~

i components and in particular, hydrocarbons. The ratio of air to natural gas utilized to produce the carbon blacks of the present ~ in~ention may preferably be from about 10:1 to about 100:1. To ! facilitate the generation of hot combustion gases, the oxidant stream may be preheated.
~ The hot combustion gas stream flows downstream from zones ¦ 10 and ll into zones 12, 18, and l9. The direction of the flow ~ of hot combustion gases is shown in the figure by the arrow.
¦ Carbon black-yielding feedstock 30 is introduced at point 32 ¦ 10 (located in zone 12), and/or at point 70 (located in zone ll).
Suitable for use herein as carbon black-yielding hydroca~bon feedstocks, which are readily volatilizable under the conditions of the reaction, are unsaturated hydrocarbons such as acetylene;
olefins such as ethylene, propylene, butylene; aromatics such as benzene, toluene and xylene; certain saturat~d hydrocarbons; and ;~other hydrocarbons such as kerosenes, naph~halenes, terpenes, ethylena tars, aromatic cycle stocks and the like.
-The distance from the end of the zone of converging diameter 11 to point 32 is shown as F-l. Generally, carbon black-yielding feedstock 30 is injected in the ~orm of a plural~ty of streams which penetrate into the interior regions of the hot combustion gas stream to insure a high rate of mixing and shearing of the carbon black-yielding feedstock by the hot combustion gases so as to rapidly and completely decompose and convert the feedstock to carbon black.
uxiliary hydrocarbon is introduced at point 70 through ~prob~ 72 or through auxiliary hydrocarbon passages 75 in the ;walls which form the boundaries of zone 12 of the carbon black forming process or through auxiliary hydrocarbon passages 76 in the walls which form the boundaries of zones 18 and/or 19 of the carbon black forming process. The auxiliary hydrocarbon may be introduced at any location between the point immediately after the initial combustion reaction of the first-stage fuel and the point immediately before the er.d of formation of carbon black provided that unreacted auxiliary hydrocarbon eventually enters ~;

~094/05732 2 1 2 1 6 ~ 3 PCT~US93/08129 _g _ the reaction zone.
The distance from point 32 to point 70 is shown as H-l.
In the Examples described herein, the auxiliary hydrocarbon was introduced through either three or four orifices in the same axial plane as the carbon black yielding feedstock streams. The orifices are arranged in an alternating pattern, one feedstock, the next auxiliary hydrocarbon, spaced evenly around the outer periphery of section 12. As will be noted, however, this is merely exemplary and is not intended to be limiting of the methods usable for introducing auxiliary hydrocarbon.
The mixture of carbon black-yielding feedstock and hot combustion gases flows downstream through zone 12 into zone 18 and then into zone 19. Quench 60, located at point 62, injecting quenching fluid 50, which may be water, is utilized to stop chemical reaction when carbon blacks are formed. Point 62 may be determir.ed in any manner known to the art for selecting the position of a quench to stop pyrolysis. One method for -~ ~ determining the position of the quench to stop pyrolysis is by determining the point at which an acceptable toluene extract level for the carbon black is reached. Toluene extract level may be measured by using ASTM Test D1618-83 "Carbon Black Extractables - Toluene Discoloration~. Q i9 the distance from the beginning of zone 18 to quench point 62, and will vary according to the position of Quench 60.
25~ After the mixture of hot combustion gases and carbon ; ~ :
black-yielding feedstock is quenched, the cooled gases pass - downstream into any conventional cooling and separating means whereby the carbon blacks are recovered. The separation of the carbon black from the gas stream is readily accomplished by conventional means such as a precipitator, cyclone separator or bag filter. This separation may be followed by pelletizing using, for example, a wet pelletizer.
~; The following testing procedures are used in evaluating theanalytical and physical properties of the carbon blacks of the present invention.

.
:,:

W094/05732 2 1 2 1 6 9 3 -lo- PCT/US93/08 ~

Iodine adsorption number of the carbon blacks (I2 No.) was I determined according to ASTM Test Procedure D 1510. Tinting ¦ strength tTint) of the carbon blacks was determined according to ASTM T~st Procedure D3265-85a. The DBP (dibutyl phthalate value) of the carbon blacks was determined according to the procedure set forth in ASTM D3493-86. The cetyl-trimethyl ammonium bromide absorption value (CTAB) of the carbon blacks was determined according to ASTM Test Procedure D3765-85.
Dmode, and Dst of the carbon blacks were determined from a histogram of the weight fraction of carbon black versus the Stokes diameter of the carbon black aggregates, as show~ in Figure 2. The data used to generate the histogram are determined by the use of a disk centrifuge such as the one manufactured by Joyce Loebl Co. Ltd. of Tyne and Wear, United Kingdom. The following procedure is a modification of the procedure described in the instruction manual of the Joyce Loebl diSk centrifuge file reference DCF 4.008 published on February 1, 1985, the teachings of which are hereby incorporated by reference, and was used in determining the data.
The procedure is as follows. 10 mg (milligrams) of a carbon black sample are weighed in a weighing vessel, then added to 50 cc of a solution of 10% absolute ethanol and 90% distilled water which is made 0.05% NONIDET P-40 surfactant (NONIDET P-40 is a registered trademark for a surfactant manufactured and sold by Shell Chemicai Co.). The resulting suspension is dispersed 1: ~
by means of ultrasonic energy for 15 minutes using Sonifier Model No. W 385, manufactured and sold by Heat Systems Ultrasonics Inc., Farmingdale, New York.
Prior to the disk centrifuge run the following data are entered into the computer which records the data from the disk centrifuge:
1. The specific gravity of carbon black, taken as 1.86 g/cc;
~2. The volume of the solution of the carbon black -~ 35 dispersed in a solution of water and ethanol, which in this ~N094/05732 -1 1 2 1 2 1 ~ 9 3 PCT/US93~08129 instance is 0.5 cc.;

3~ The volume of spin fluid, which in this instance is lO
cc of water;

4. The viscosity of the spin fluid, which in this instanc is ta~en as 0.933 centipoise at 23 degrees C;

5. The density of the spin fluid, which in this instance is 0.~975 g/cc at 23 degrees C;

6. The disk speed, which in this instance is ~000 rpm;

7. The data sampling interval, which in this instance is l second.
The disk centrifuge is operated at 8000 rpm while' the stroboscope is operating. lO cc of distilled water are injected into the spinning disk as the spin fluid. The turbidity level is set to 0; and l cc of the solution of lO~ absolute ethanol and gO~ distilled water is injected as a buffer liquid. The cut and boost buttons of ~he disk centrifuge are then operated to produce a smooth concentration gradient between the spin fluid and the buffer liquid and the gradient is monitored visually.
When the gradient becomes smooth such that ~here is no distinguishable boundary between the two fluids, 0.5 cc of the dispersed carbon black in aqueous ethanol solution is injected into the spinning disk and data collec~ion is started : ~ !
immediately. If streaming occurs the run is aborted. The disk is spun for 20 minutes following the injection of the dispersed carbon black in aqueous ethanol solution. Followin~ the 20 minutes of spinning, the disk is stopped, the temperature of the spin fluid is measured, and the average of the temperature of the spin fluid measured at the beginning of the run and the temperature of the spin fluid measured at the end o~ the run is entered into the computer which records the data from the disk centrifuge. The data is analyzed according to the standard Stokes equation and is presented using the following ~- definitions:
~-~ Carbon black aqgregate - a discrete, rigid colloidal entity that is the smallest dispersible unit; it is composed of W~94/05732 2 1 2 1 6 9 ~ -12- PCTJUS93/0~

extensively coalesced particles;
Stokes diameter - the diameter of a sphere which sediments in a viscous medium in a centrifugal or gravitational field according to the Stokes equation. A non-spherical object, such as a carbon black aggregate, may also be represented in terms of the Stokes diameter if it is considered as behaving as a smooth, rigid sphere of the same density, and rate of sedimenta~ion as the object. The customary units are expressed in nanometer diameters.
Mode (Dmode for reporting purposes) - The Stokes diameter at the point of the peak (Point A of Figure 2 herein~ of'the distribution curve for Stokes diameter.
Median Stokes diameter - ~Dst for reporting purposes) the point on the distribution curve of Stokes diameter where 50% by weight of the sample is either larger or smaller. It therefore represents the median value of the determination.
Tha modulus, tensile and elongation of the EPDM
; compositions were measured by the procedure set forth in ASTM
D412-87.
The Shore A Hardness of the EPDM compositions was determined according to the procedure set forth in ASTM D-2240-86.
Rebound data for the EPDM compositions was determined according to the procedure set for~h in AS~M D1054, utilizin~ a ZWICK Rebound Resilience Tester, Model 510~, manufactured by Zwick of America, Inc., Post Office Box 997, East Windsor, Connecticut 06088. Instructions for determining the rebound values accompany the instrument.
;~ The Compression set of the EPDM compositions was determined according to the procedure set forth in ASTM D395, wherein the composition was tested at 1509 F for 70 hours.
The extrusion shrinkage of the EPDM compositions was determined by the procedure set forth in ASTM D-3674 The :~
extrusion shrinkage was measured on the BRABENDER extruder at 1009 C and 50 rpm using a 5 mm diameter die.
~' : ':
:

21216~3 -~094/05732 -13- PCT/US93/08129 The viscosity of the EPDM compositions was determined by the procedure set forth in ASTM D-16~6 using a Monsanto MPT
capillary rheometer maintained at 100~ C using a die having a ratio of L/D~=16 and D=0.0787mm (millimeter). The shear rate ranged from 10 to lS0 l/seconds.
Mixing energy is the total amount of ene,rgy put into the compositions which is determined by integrating the mixing torque curve over the course of the mixing cycle, described hereinafter.
Cure characteristics of the EPDM compositions were measured using a Monsanto MDR curemeter maintained at 160 D C. The time to reach 90~ cure reaction (t'90), the total torque change during cure reaction (~L) and cure rate index (CRI; (CRI =
,~ l/(t'90 - tsl) x 100) where tsl = the time when the torque level is 1 unit above minimum torque (tsl is also referred to as scorch timQ)~ are reported for the example EPDM compositions.
;~ The tests were conducted according to the instructions furnished with the Monsanto MDR curemeter.
Composition resistivity was measured on plaque samples 2 inches wide by 6 inches long by 0.085 inch thick. The plaques ; were painted on both ends with a half inch width o~ sil~er paint. The sample was conditioned to produce a stable reading ~ by cycling from room temperature to lOOY C and back to room -~ te~perature, followed by aging at 90~ C for 24 hours. The stabilized resistivity was measured at the end of the aging cycle, and once again after the sample was allowed to cool back to room temperature.
~ , The effectiveness and advantages of the present invention ,' ~ will be further illustrated by the following examples.
: .
EX~MPLES 1-8 Examples of the novel carbon blacks of the present invention were prepared in a reactor generally described herein, ~, and as depicted in Figure 1, utilizing the reactor conditions and geometry set forth in Table 3. The fuel utilized in the ~:

W094/05732 2 1 2 1 6 9 ~ PCT/~Sg3/08~

combustion reaction was natural gas. The auxiliary hydrocarbon used was also natural gas. The liquid feedstock utilized had the properties indicated in Table 2 below:

Tabl~ 2 r ¦ FEEDSTOCKPROPERTIES
. , , .-. , , ,~
: 5 Hydrogen/Carbon 0.93 Ratio Il Hydrogen (wt%) 7.19 Carbon twt~) 92.1 Sulfur (wt%) 0.3 Nitrogen (wt%) 0.41 : A.P.I. Gravity 15.6/15.6~ C -1.6 (60/60~ F~
~ASTM D-287] . l ~: _ __~ I
15: Speci~ic Gravity ~:: 15.5/15.6~ C 1.092 : (60/60 ~F) : ~ASTM D-2873 Viscosity, SUS 5 0 (54.4 C) m2/s 2.6 x ~0~
tASTM D-88~ . :
Viscosity, SUS 5 . 2 X 10-6 (98.9-C) m2/s . ~ASTM D-88]
BMCI (Visc-Grav) 133 : The reactor conditions and geometry were as set forth in Table : ~ .
3 below.

:; ~' .
- :

2121~93 .~YO94/0~732 PCT/US93/08129 Table 3 Reactor Geometry and Operating Conditions.

~ Examp~e No. 1 1 1 2 1 3 1 4 1 5 1 6 ¦ 7 ¦ ~
_ _ D~l ~m) 0.180.18 0.18 0.18 0.18 _0.18 0.18 0.18 0-2 ~m) 0.110.11 0.11 0.11 0.13 O.lt 0.13 ~ ~ 0.13 D-3 ~m~ 0.69 0.69 0.69 0.69 0.91 0.690.69 0.69 D-4 ~m) 0.25 0.25 0.25 0.25 0.26 0.250.25 0.36 D-5 ~m) 0.69 0.69 0.69 0.69 0.33 0.690.69 0.69 0-6 (m) 0.69 0.69 0.69 0.69 0.91 0.690.69 0.69 lO D-7 (m) 0.69 0.69 0.69 0.69 0.91 0.690.69 0.69 L-l ~m) 0.61 0.61 0.61 0.61 0.61 3.610.61 0.61 L-2 (m) 0.30 0.30 0.30 0.30 0.30 0.300.30 0.30 L-3 (m) n.23 0.23 0.23 0.23 0.23 0.230.23 0.23 L-4 (m) 0.30 0.30 0.30 0.30 0.30 0.}00 30 0.14 15 L-5 (m) 0.10 0.10 0.10 0.10 0.23 0.100.10 0.10 L-6 (m) 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 L -7 (m) 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 F-1 (m) 0.11 0.11 0.11 0.11 0.11 0.110.11 0.11 0 (m) 7.93 7.93 7.93 7.93 7.93 7.9319.8 7.93 2 0 CollbUStiOr~ Ai r 0.373 0.6340.634 0.63~0.6340.634 0.448 0.634 ( SCMS ) Co~ i r rjs 755 7S5 755 755 755 755 755 Preheat (K) Surner hat. Gas 0.9 2.0 2.0 2.0 1.8 2.5 1.4 2.0 2 5 t102 x SCMS) Feedstock 0.198 0.218 0.198 0.1980.185 0.1980.1980.206 Injection Orifice Dia (cm) 3 0 Uo. Feed~tock 3 3 3 3 S 3 4 4 Injection F ~ sto~ R;te 1.3 2.1 1.9 2.3 1.3 1.9 1.6 2.1 3 5 Feed~tock Temp483 463 451 438 467 439 467 415 (10 1~- Conc. (gtm~) 0.0 U.1 81.0 0.0 388.011.4 0.8 20.3 ~ux. NC 0.635 0.635 0.635 0.6350.635 0.6350.6350.635 Injection 4 0 Orifice Di meter (cm) ~o. ~ux. IIC 3 3 3 3 4 3 4 4 Inlection Orifices ~) 4 5 I ~ HC R-te 2.4 3.5 2.1 3.9 3.1 2.1 1.7 0.0 ~10~ x SCMS) I
Primary Combus- 400 400 400 400 300 325 400 400 ion ~X) Over-ll Carbus- 21.7 22.5 25.4 21.5 22.925.5 21.4 25.0 5 0 ion (X) ~*) - The feedstock and auxiliary hydrocarbon orifices were arranged in the same axial plane in an alternating sequence around the periphery of the : reactor.
HC = hydrocarbon W094/05732 2 121 6 9 3 -16- PCT/US93/081~

The carbon blacks produced in runs 1-8 were then analyzed according to the procedures described herein. The analytical properties of the carbon blacks were as set forth in Table 4.

Table 4 Carbon Black Analytical Properties Exunple 1 2 3 i 4 5 6 7 8 _ 22.1 13.6 28.0 16.3 40.7 28.8 28.7 57.9 DBP (c~/1OOg)132.537.1 35.8 84.6 43 1 ~4.5 119,5 95.8 ..
CTAB (m~/g) 25.3 17.3 29.8 18.7 45.1 2~.7 27.8 53.1 Tint (5) 33.0 33.4 54 7 37.5 85.6 45.7 33.5 74.2 1 0 Dmode (nm) 289 246 212 276 176 21~2 279 140 Dst (nm) 459 390 300 492 240 312 486 180 ~-Ra~io 1 59 1.58 1.42 1.78 1.36 1.47 1.74 1.29 ~: These carbon blacks and four control carbon blacks were utilized in the following examples. The four control carbon : 15 blacks utilized, A-D, had the analytical properties shown below in Table 5:
;: ~
T~ble S Control Carbon Black Analytical Properties : Control~ A ~ B ¦ C D
Type ~ GPF FEF Thelrma SRF ¦¦
I2 No. 35.4 40.0 8.2 29.9 : (mg~g)~
DBP 91.0 111.7 37.5 68.5 ~cc/lOOg) CTAB (m~/g)~ 35.9 44.3 9.9 30.1 Tint (%) 57.8 64.6 21.7 51.6 : Dmode (nm) 206 144 416 256 . Dst (nm) 220 186 492 288 M-Ratio ~ 1.07 1. 29 1.18 1.12 GPF = general purpose furnace FEF = fast extruding furnace Thermal = carbon black produced by a thermal proce$s SRF - semi reinforcing furnace ~, : ~:

--~094/05732 2 1 2 1 6 9 3 PCT/US93/0812~

EXA~PLE 9 The carbon blacks of the present invention produced in example runs 1-8 were incorporated into EPDM (ethylene-propylene diene polymethylene) compositions and compared to EPDM compositions incorporating the four control carbon blacks. The EPDM compositions were prepared utilizing each of the carbon black samples in an amount of 200 parts by weight in ~ne EPDM Composition Formulation shown below in Table 6.
Table 6 - EP~M COMPOSITION FORMUL~TION
i INGREDIENTPART BY WEIGHT
EPDM lO0 Carbon Black 200 Sunpar 2280 Oil l00 : Zinc Oxide _ 5 Stearic Acid l __ TMTDS 2.7_ _ Butyl Zimate 2.7 _ ~: Methyl Zimate 2.7 . Sulfur 0.5 _ _ : 20 l Sulfasan R l.7 EPDM - EXXON VISTALON05600`, manufactured and sold ~ by EXXON Corporation, Houston, Texas;
:~ Sunpar 2280 - A trademarked oil manufactured and sold by Sun Oil Company;
TMTDS - Tetramethylthiuram disulfide;
Butyl Zimate - A trad~marked zinc dibutyldithiocarbamate manufactured and sold by R. T. Vanderbilt Co.;
Methyl Zimate A trademarked zinc dimethyldithiocarbamate manufactured and sold by R. T. Vanderbilt Co.;
Su~fasan R - A trademarked 4,4'-dithiodimorpholine, manufactured and sold by Monsanto Co., St.
Louis,-Missouri :~ .
;~ 35 The EPDM compositions were produced as follows.
A Banbury BR mixer was started and maintained at a temperature o~ 45Y C and a rotor speed of 77 RPM. EPDM was added to the mixer and mixed for approximately 30 seconds. The Sunpar 2280 , WQ94/05732 2 1 2 1 6 9 3 - 18 - P~T/VS93/081~

oil, zinc oxide and stearic acid, were added to the EPDM and mixed for approximately 2 additional minutes. The carbon black was added to the mixture and the temperature of the mixing chamber was cooled and maintained at a temperature of below approximately 135~ C. The carbon black containing EPDM
mixture was mixed for approximately 4 1/2 minutes and then the curing agents, TMTDS, Butyl Zimate, Methyl Zimate, Sulfur and Sulfasan R, were added to the mixture. The resulting mixture was mixed for approximately l l/2 minutes while the temperature was maintained at below approximately 135~ C. ~ The batch composition was then discharged from the mixer and analyzed by the techniques described herein.
; The EPDM compositions produced using the carbon hlacks of the present invention produced in runs 1-8 described herein had the performance characteristics set forth below in Table 7.
The EPDM compositions incorporating the control carbon :::
blacks A-D were also evaluated according to the procedures described herein. The results are set forth in Tables 8-13 below, where comparisons between EPDM compositions containing carbon blacks of thP present invention and EPDM compositions containing the most appropriate control carbon black are made.
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~ ~ 0 94/05732 2 1 2 1 6 9 3 PC~r/USg3/08129 ~able 7 Co~parison of EPD~ Co~position Performance.

¦Ex~mple No ¦ 1 ¦ 2 ¦ 3 ¦ 4 ¦ 5 ¦ 6 ¦ 7 ¦ 8Carbon B(ack AnalYtical Pro~erties-I . . _ S lodir,e NuTber (~gtg) 22.1 13.6 28.0 16.3 40.7 28.ô 28.7 57.9 l _ DBP ~cc/100g) _ 132.537.1 35.8 84.o6 43.1 64.5 119.5 95.8 CT~B (~ ~9) 25.3 17.3 29.ô 18.7 45.1 28.7 27.8 53.1 Tint ~X) 33.0 33.4 s4.r 32 5 85.6 45.7 42.3 74 2 Mode Stokes Dia. (r~) 289 246 212 276 176 212 252 10 IO Median Stokes Dia. 459 390 300 492 240 312 348 180 ~r~n? _ ~-Ratio ~Median/~ode 1.59 1.58 1.42 1.78 1.36 1.47 1.38 1.29 Stokes) EPDK ComPosition Performsnce at Z00 phr:
1 5 Visclsity ~P~-S) a10 1630012100 10900 18000 14100 16000 22900 23700 sec Visclosity ~Pa-S) ~1S0 2600 1540 1590 1920 1 n 0 1790 2790 3130 ~ixing Energy (MJ/m3) 1300 91B 876 1110 943 1139 1348 1571 2 ol Extrusion Rate (g~min) 37.0 35.3 42.3 40.0 34.8 34.2 47.1 50.
Extrusion Shrinkage 12.5 37.6 43.0 21.7 41.1 27.1 13.8 12.5 ~ ~ (X) : __ t'90 (min) 8.2311.811.9 9.7 9.6 10.2 10.5 9.9 r ~L (g-~) 238 Z34 Z06 zn 271 247 _308 Z1O
~ ~ _ _ 2 5 ~ordness (Shore ~) 79 57 65 69 65 67 76 79 E100 (104 x ~/m2) 662 184 175 392 192 299 540 628 Tensile (10~ x ~/m2) 1069 779 974 925 100. 977 929 lZ68 . _ ¦Elong. at Breok ~%) 243 592 623 389 595 397 232 23r Rebound ~X) ~ 39 51.7 43.7 47.4 34.2 44.2 40.0 30.5 3 0 ItomPression Set ~X) 55 56 50 52 65 54 54 58 ~70 hrs, 150-C~
¦Resistivity ~Q-cm) n: 9 800 __ 106 208 83 24 25-c _ Qesistivity ~n~rm~ 12718200 _ 153 178 104 43 ...
3 5 la9O-C _ not evaluated ~::

W094/~5732 2 1 2 1 6 9 ~ P~T/US93/081~

~able 8. Comparison of EPDM Composition Performance . .
Example No. 1 7 Control _ _ Carbon Black Analytical Properties:
Iodine Number (mg/gj22.1 228.7 40.0 DBP (cc~lOOg) 132.5_ 119.5 111.7 CTAB (m /g) 25.327.8 44.3 Tint ~%) 33.042.3 64.6 Mode~Stokes Dia. 289 252 144 (nm) Median Stokes Dia. 459 348 lB6 (nm) .
M-Ratio (Median/Mode 1.591.3~ 1029 Stokes) EPDM Composition : 15 Performance at 200 p~ .r: _ _ _ Viscosity (Pa-S) ~ 1630022900 30700 10 sec~1 . . , Viscosit~ (Pa-S) @ 26002790 3450 150 sec . _ Mixing Energy 13001348 1561 ~/m~ ) ~ . __ I
Extrusion Rate 37.047.1 44.7 ~g/min) .
Extrusion Shrinkage 12.513.8 18.2 (%) _ .
~` : t'90 (min) 8.2310.5 7.45 : I~L ~g-m) _ 23B 308 293 1 Hardness (Shore A~ 79 76 82 ~ IE100 (104 X N/m~) 662~540 650 ¦Tensile tlO4 x N/m~) 1069 929 1103 ¦Elong.~at Break (%) 243 232 184 ; ~Rebound (%) 39 40.0 31.0 Compression Set (~) 55 54 57 (70 hrs, 150-C) Resistivity (n-cm) 72 24 43 Resistivity (n- cm~ 127 43 69 .

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~ ^-~094/05732 2121 6 93 PCT/US93/08129 These results set forth in Table 8 indicate that at a carbon black level of 200 phr the EPDM compositions incorporating the carbon blacks of the present invention have lower viscosity and lower mixing energy. Therefore the EPDM
compositions incorporating the carbon blacks of the present invention exhibit better processing characteristics than the EPDN compo~itions incorporating the control carbon bla~ks.
Table 9. Comparison of EPDM Composition Performance Example No. 1 Control .,. j Carbon Black Analytical Properties: I
Iodine Number (mg/g) 22.1 40.0 , DBP ~cc/lOOg) 132.5 111.7 CTAB (m /g) 25.3 44.3 Tint (~) 33.0 64.6 ~ 15 Mode Stokes Dia. (nm) 289 144 _ :~ Median Stokes Dia. (nm) 459 186 . I
~:: M-~atio (Median~Mode 1.59 1.29 Stokes) _ . .
: EPDM Composition Performa nce at ~ 50 phr:
- 20 V scosity (Pa-S) Q 10 12500 22200 : Viscosity (Pa-S) Q 150 1900 1940 l sec I
~ . ...................................... l Mixing Energy (MJ/m') 1010 1222 Extrusion Rate (g/min) 39 37.4 ~ ~ 17.2 19.8 ;~ t'90 (min) 9.25 8.33 :~ : ~L (g-m) 200 249 : Hardness (Shore A) 69 71 E100 (104 x N/m~) 407 376 A , Tensile (10~ x N/m~) 1145 1179 ~: Elong. at Break (%) 436 370 Rebound ~%) 46.1 35.8 Compression Set (%) (70 57 57 hrs, 150~C) -~ Resistivity (n~cm) @25 C400 88 .
: Resistivity (n- cm) Q9CC 640 118 :~

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W094/05732 2 1 2 1~ 9 3 PCT/USg3/081~
The results set forth in Table 9 show the advantage of utilizing a carbon black of the present invention in an EPDM
composition for an application where resistivity is a critical requirement. As shown in the table, at 150 phr loading, which is typical for a cooling hose application, the EPDM
composition incorporating the carbon black of the present invention exhibits a higher resistivity than the EPDM
composition incorporating the control carbon black.
Additionally, the EPDM composition incorporating the carbon black of the present invention has lower viscosity and ~; lower mixing energy than the EPDM composition incorporating the control carbon black. This indicates that EPDM
~` compositions incorporating the carbon black of the present invention will have improved processibility in comparison with EPDM compositions incorporating the control carbon black.

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~ '094~05732 2 1 2 ~ 6 g 3 PCT/US93/08129 - Table 10 Co~parison of EPDM Composition Performance.
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Example No. 6 Control D
., _ _ .
Carbon Black Analytical P ropertie s:
Iodine Number (mg/g) 28.8 29.9 _ DBP (rc/lOOg) _ 64.5 68.S
CTAB ~m /g) _ 28.7 30.1 Tint _(%) 45.7 -~51.6 I
Mode Stokes Dia. (nm) 212 256 Median Stokes Dia. ~nm) 312 _ 28B
M-Ratio (Median/Mode 1.47 1.12 Stokes) _ __ EPDM Composition Performance at 200 phr:
Viscosity (Pa-S) @ 10 16000 16600 sec-~
Viscosity (Pa~S) Q 150 1790 1880 . I
Mixing Energy (MJ/m') 1139 1091 Extrusion Rate (g/min) 34.2 36.8 Extrusion Shrinkage ~%)27.1 23.8 l t'~O~(min) 10.2 11.2 ¦
~L (g-m3 247 270 Hardness ~Shore A) 67 69 iE100 ~104 x N/m~) 299 338 ~: I - . .
~ensile ~104 X N/m~) 9775 9899 ¦Elong. at Break ~%) _ 397 4~1 ~; Rebound ~%) 4~.2 40.6 , Compression Set (%) ~70 54 57 ~ hrs, 150C) :~: .
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The results ~et forth in Table 10 indicate that the ~compression set of the EPDM composition incorporating the car~on~black of the present invention is lower than the compression set of the EPDM composition incorporating the aontrol carbon black. Thus an EPDM composition incorporating the carbon black of the present invention is more resistant to ~; 35 permanent deformation. As a result the compositions will be par~icularly advantageous for use in sealing applications such as door seals and weather stripping.

W~94/~5~32 2 1 2 1 6 9 3 -24- PCT/U~93/08 ~
Ta~le 11 - Comparison of EPDM Compocition Performance . =. .
Example No. 2 Control . . _ .
Carbon Black Analytical P ropertie s:
Iod~ne Number (mg/g) _ 13.6 8.2 DBP (cc/lOOg) 371. 37.5 CTAB (mZ/g) 17.3 Tint (~ . 33.4 . 21.7 Mode Stokes Dia. (nm) 246 416 Median Stokes Dia. (nm) 390 492 M-Ratio (Median/Mode 1.58 1.18 Stokes) .
EPDM Composition Performance at 200 phr: ¦
Viscosity (Pa~S) ~ 1012100 10400 sec , Viscosity (PaqS) @ 1501540 1490 : Mixing Energy (MJ/m') 918 799 Extrusion Rate (q/min)35.3 32.0 Extrusion Shrinkage (%) 37.6 4305 _¦ ¦
t'sO ~min) 11.8 13.2 ~: ~L (g-m) 234 220 ¦
¦; ~ Hardness (Shore A) 57 53 ~¦
E100 (104 x N/m~) 184 109 -¦¦
Tensile (10 x N/m ) 779 g33 Elong. at Break (%~ 592 794 ¦¦
ll :~ Rebound (%) 51.7 55.0 : Compression Set (~) (70 56 S4 : : hrs, 150C) ~:
~ The results set forth in Table 11 indicate that the carbon , ~ .
blacks of the present invention provides improved reinforcement properties, particularly higher modulus and higher hardness to EPDM compositions when compared to thermal carbon blacks. Thus the carbon blacks of the present , invention advantageously provide furnace carbon black replacements for thermal carbon blacks or carbon black blends containing thermal carbon blacks.

2121~9~
-~V094/05732 -25- PCT/US93/OX129 Ta~le 12 Comparison of EPDM Composition Performance.
- __ Ex~mple No. 3 4 5 i Control C Control D
_ CArbon Blne~ Analyticnl Properties:
~lodine Number tmgtg) 28.0 16.3 40.7 8.2 29.9 ¦DBP ~cc/lOOg~ 35.8 84.6 43.1 37.568.5 CTAB (m~g) 29.8 18.7 45.1 9.9 30.1 Tint (Z) 54.7 32.5 85.6 21.751.6 ~ode Stokes Dia. (nm) 212 276 176 416 256 Medi~n Stokes Din. (nm) ~ 300 492 240 _ 49Z 28B
1 0 -RDtio (Median/~ode Stokes~ 1.42 1.78 1.36 _ 1.18 1.1Z EPD~ ComDo~ition Perfor ance ~t Z00 Dhr:
Viscosity (Pa-S) a 10 sec~' 10900 18000 14100 10~00 16600 Viscosity (Pa-S) ~ 150 sec ~ 1590 1920 1720 1490 1880 Hixing Energy (MJtm') 876 1110 943 1091 1 5 Extrusion Rate (g/min) 42.3 40.0 34.8 32.0 36.8 Extrusion Shrinkage ~%) 43.0 21.7 41.1 43.5 23.8 t'90 (min) 11.9 9.7 9.6 13.2 11.Z
~L (g-m) ~ 206 272 271 220 270 H~rdness (Shore ~) 65 69 65 53 69 E100 (104 X N/m~) 175 392 192 109 338 Tensile (1D~ x U/m~) 974 925 1009 933 989 E~ong. ~ ~reak (%) 623 389 595 794 421 Rebound (%) 43.7 47.4 34.2 55.0 40.6 Compression Set (%) (70 hrs150-C) 50 52 65 54 57 , The results set forth in Table 12 indicate that 'he carbon blacks of the present invention can replace the use of blends of thermal and SRF type carbon blacks to provide a satisfactory degree of performance characteristics. EPDM
compositions incorporating the carbon black of Example 5 also yield profiles having textured matte finishes when extruded or shaped.

W094/0~732 2 1 2 1 6 9 ~ -26- PCT/US93/0~ ~
Table 13 Comparison of EPDM Composition Performance.
Example No. ¦ 8 ¦Control A¦Control Carbon Black Analytical Properties:
Iodine Number (mg/g) 57.935.4 40.0 DBP (cc/lOOg) 95.891.0 111.7 CTAB (m~/g) 53.1~ 35.9 44.3 Tint (%) 74.257.8 64.6 Mode Stokes Dia. (nm) 140206 144 Median Stokes Dia. 180~20 186 (nm) M-Ratio (Median/Mode 1.291.07 1.29 Stokes) ~ ~
EPDM Composition Perfo rmance at 200 phr:
Viscosity ~Pa-S) @ 10 1 23700 1 24000 1 30700 .

Mixing Energy ~MJ/m')1581 1252 1561 Extrusion Rate 50.6 41.1 44.7 (g/min) ~
Extrusion~Shrinkage 12.5 15.9 18.2 _ 90 (min) 9.9 7.41 7.45 ~L (g-m) 218 299 293 Hardness (Shore A) 79 75 82 E100 (IO4 x N/m~) 628 493 650 Tens le (104 X N~m~) 1268 1030 1103 Elong. at Break (%) 237 288 184 Re~ound (~) 30.5 34.5 31.0 Compression Set (%) 58 50 57 (70 hrs, 150-C) The results set forth in Table 13 indicate that the EPDM
composition incorporating the carbon black of the present invention has a higher extrusion rate than the EPDM
compositions incorporating the control carbon black. Thus, EPDM compositions incorporating the carbon blacks of the present invention may be extruded at higher throughputs than EPDM compositions incorporating the control carbon blacks.
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The EPDM composition incorporating the carbon black of -~ 40 the present in~ention also has a lower extrusion shrinkage and ~therefore will have better dimensional control during the ~094/05732 2 1 2 1 ~ 9 3 PCT/US93/08129 extxusion operation than the EPDM compositions incorporating the control carbon blacks~
These results also indicate that the EPDM composition incorporating the carbon black of the present invention has good overall physical properties. Additionally, the carbon blacks of the present invention have a unique ~ombination ~f surface area and s~ructure that results in the carbon blacks being useful in preparing EPDM compositions that are to be UHF
cured.
It should be clearly understood that the forms of the, present invention herein described are illustrative only and :~ are not intended to limit ~he scope of thP invention.

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Claims (23)

WO 94/05732 PCT/US93/08???

We Claim

1. A carbon black having an I2No. of 17-23 mg/g and a DBP of 115-150 cc/100g.

2. The carbon black of claim 1 wherein the I2No. is 20 mg/g.

3. A carbon black having an I2No. of 10-19 mg/g, and a DBP of 70-95 cc/100g.

4. The carbon black having an I2No. of 12-20 mg/g and a DBP of 34-65 cc/100g.

5. The carbon black of claim 4 wherein the I2No. is 14-18 mg/g and the DBP is 36-55 cc/100g.

6. The carbon black of claim 5 wherein the DBP is 36-42 cc/100g.

7. The carbon black of claim 5 wherein the DBP is 45-55 CC/100g.

8. A carbon black having an I2No. of 28-43 mg/g and a DBP of 28-47cc/100g.

9. The carbon black of claim 8 wherein the I2No. is 30-42 mg/g.

10. A carbon black having an I2No. of 8-32 mg/g, a DBP
of 28-150 cc/100g and an M-Ratio of 1.25-2.00.

11. A carbon black having an I2No. of 33-70 mg/g, a DBP
of 28-60 cc/100g and an M-Ratio of 1.25-2.00.

12. A carbon black having an I2No. of 42-50 mg/g, a DBP

of 61-105 cc/100g and an M-Ratio of 1.25-2.00.

13. A carbon black having an I2No. of 51-62 mg/g, a DBP
of 61-125 cc/100g and an M-Ratio of 1.25-2.00.

14. A carbon black having an I2No. of 63-70 mg/g, a DBP
of 61-105 cc/100g and an M-Ratio of 1.25-2.00.

15. A composition of matter comprising a material selected from the group consisting of rubbers and plastics, and a carbon black of claim 1.

16. A composition of matter comprising a material selected from the group consisting of rubbers and plastics, and a carbon black of claim 3.

17. A composition of matter comprising a material selected from the group consisting of rubbers and plastics, and a carbon black of claim 4.

18. A composition of matter comprising a material selected from the group consisting of rubbers and plastics, and a carbon black of claim 8.

19. A composition of matter comprising a material selected from the group consisting of rubbers and plastics, and a carbon black of claim 10.

20. A composition of matter comprising a material selected from the group consisting of rubbers and plastics, and a carbon black of claim 11.

21. A composition of matter comprising a material selected from the group consisting of rubbers and WO 94/05732 PCT/US93/081??

plastics, and a carbon black of claim 12.

22. A composition of matter comprising a material selected from the group consisting of rubbers and plastics, and a carbon black of claim 13.

23. A composition of matter comprising a material selected from the group consisting of rubbers and plastics, and a carbon black of claim 14.