Title of Invention	CARBON BLACK.
Abstract	A carbon black having attached thereto at least one organic group selected from the group consisting of an N-(4-thiocyanate alkyl)succinimide, N-(4- thiocyanate aryl) succinimide, N-(4-thiocyanate alkyl)amide and N-(4- thiocyanate aryl)amide group.

Full Text

Carbon black The invention concerns a carbon black, a process for its production and its use. Carbon blacks having organic groups are known from DE 10012783, wherein the organic group contains at least one substituted C-C single or double bond, is linked to the carbon black by means of the two carbon atoms in the C-C single or double bond and at least one carbon atom in the C-C single or double bond contains at least one activating substituent. A process for the surface modification of carbon-containing material having aromatic groups by electrochemical reduction of a diazonium salt is known from EP 0569503. The furnishing of carbon black with organic groups by linking the organic groups to the carbon-containing material by diazotisation (WO 96/18690) or by bonding the organic groups to the carbon black by means of reactions with radical formers (Ohkita K., Tsubokawa N., Saitoh E., Carbon 16 (1978) 41, DE 10012784.3) is also known. A disadvantage of the known carbon blacks is that when surface-modified carbon blacks are used in rubber compounds, the hysteresis (correlated with rolling resistance) and/or the dynamic rigidity (correlated with handling properties) deteriorates. The object of the present invention is to provide a carbon black that in a rubber compound has a higher or an equal dynamic rigidity (E* 60°C) combined with reduced hysteresis (tan δ 60°C). The invention provides a carbon black having organic groups, which is characterised in that the organic group contains a thiocyanate group. In a preferred embodiment the organic group can be a thiocyanate alkyl or thiocyanate aryl group, preferably an N-(4-thiocyanate alkyl)succinimide, N-(4-thiocyanate aryl)succinimide, N-(4-thiocyanate alkyl)amide or N-(4- thiocyanate aryl)amide group, particularly preferably an N- (4-thiocyanatophenyl)succinimide or N-(4- thiocyanatophenyl)amide group. The alkyl group can be a divalent branched or unbranched, saturated or unsaturated hydrocarbon having 1 to 20 C atoms. The aryl group can be a phenyl or naphthyl group. The invention also provides a process for the production of the carbon black having organic groups according to the invention, which is characterised in that carbon black is reacted with organic compounds containing a C-C double or triple bond, which is not part of an aromatic system, whose C-C double or triple bond is activated by at least one substituent, and the organic compound contains at least one thiocyanate group. Activating substituents can be acceptor substituents. Acceptor substituents can be -COOR, -CO-R, -CN, -SO2R, -SO2OR, -CO-X-CO- where R = H, -NH-R1, alkyl, aryl or functionalised alkyl or aryl, X = 0 or N-R1, R1 = alkyl, Y- functionalised alkyl, polymers, cyclic organic groups, aryl or Y-functionalised aryl in the form Ar-Yn (n=l-5), Y = -OH, -SH, -SO3H, -SO3M, -B(0H)2, -0(CH2-CH2-O)nH, -COOH, -NH2, -NR2, -N((CH2-CH2-O)nH)2, CON((CH2-CH2-O)nH)2, trialkoxysilyl, perfluoroalkyl, R1, -NH3+, -NR3+, -SO2-NR2, -N02, -Cl, -CO-NR2, -SS- or -SCN, M = metal, for example alkali+ or alkaline-earth++, or NRV where R2=H, alkyl or aryl. In a preferred embodiment the organic compound can contain a thiocyanate alkyl or thiocyanate aryl group, preferably an N-(4-thiocyanate alkyl)succinimide, N-(4-thiocyanate aryl)succinimide, N-(4-thiocyanate alkyl)amide or N-(4- thiocyanate aryl)amide group, particularly preferably an N- (4-thiocyanatophenyl)succinimide or N-(4- thiocyanatophenyl)amide group. The carbon blacks having organic groups according to the invention can be produced by reacting the starting carbon blacks with N-(4-thiocyanatophenyl) maleic acid imide or N- (4-thiocyanatophenyl) maleic acid amide. One possible reaction mechanism could be: N-(4-thiocyanatophenyl) maleic acid imide and N-(4- thiocyanatophenyl) maleic acid amide can be produced from maleic anhydride and thiocyanatoaniline. Furnace black, gas black, channel black, lamp black, thermal black, acetylene black, plasma black, inversion blacks, known from DE 195 21 565 and DE 19839925, Si- containing carbon blacks, known from WO 98/45361 or DE 19613796, or metal-containing carbon blacks, known from WO 98/42778, arc black and carbon blacks that are secondary products of chemical production processes can be used as starting carbon blacks. The carbon black can be activated by preliminary reactions, by oxidation for example. Coloured carbon blacks can be used. Other carbon blacks can be: conductive carbon black, carbon black for UV stabilisation, carbon black as a filler in systems other than rubber, for example in bitumen, plastics, carbon black as a reducing agent, in metallurgy. Another process for the production of the carbon black having organic groups according to the invention is characterised in that carbon black is reacted with a diazonium salt and the diazonium salt contains a thiocyanate group. The diazonium. salt can be produced by reacting a primary amine with sodium nitrite, preferably in acid solution. 4- Thiocyanatoaniline, for example, can be used as the primary amine. The invention also provides a rubber compound that is characterised in that it contains a rubber or a blend of rubbers and the carbon black having organic compounds according to the invention. Natural rubber and/or synthetic rubbers can be used as the rubber. Preferred synthetic rubbers are described for example in W. Hofmann, Kautschuktechnologie, Genter Verlag, Stuttgart 1980. They can include, inter alia, polybutadiene (BR) polyisoprene (IR) styrene/butadiene copolymers having styrene contents of 1 to 60, preferably 5 to 50 wt.% (SBR) isobutylene/isoprene copolymers (IIR) butadiene/acrylonitrile copolymers having acrylonitrile contents of 5 to 60, preferably 10 to 50 wt.% (NBR) ethylene/propylene/diene copolymers (EPDM) and blends of these rubbers. In a preferred, embodiment the rubbers can be capable of vulcanisation with sulfur. The rubber compounds can contain 10 to 150 parts by weight of carbon black having organic groups, the parts by weight relating to 100 parts by weight of rubber. The rubber compounds can contain organosilanes in a quantity of 0.1 to 15 wt.%, relative to the quantity of filler used. Alkyl silanes, for example octyl trimethoxysilane, hexadecyl trimethoxysilane, octadecyl trimethoxysilane, propyl triethoxysilane or octyl triethoxysilane, or organopolysulfane silanes, for example bis-(triethoxysilylpropyl)tetrasulfane or bis- (triethoxysilylpropyl)disulfane, can be used as organosilanes. The rubber compounds according to the invention can contain other known rubber auxiliary substances, such as e.g. crosslinking agents, vulcanisation accelerators, reaction accelerators, reaction retarders, antioxidants, stabilisers, processing aids, plasticisers, waxes, metal oxides and activators, such as triethanolamine, polyethylene glycol or hexanetriol. The rubber auxiliary substances can be used in conventional quantities, which are governed inter alia by the intended application. Conventional quantities are for example quantities of 0.1 to 50 wt.%, relative to rubber. Sulfur or organic sulfur donors can be used as crosslinking agents. The rubber compounds according to the invention can also contain vulcanisation accelerators. Examples of suitable vulcanisation accelerators are mercaptobenzothiazoles, sulfenamides, guanidines, thiurams, dithiocarbamates, thio ureas and thiocarbonates. The vulcanisation accelerators and sulfur can be used in quantities of 0.1 to 10 wt.%, preferably 0.1 to 5 wt.%, relative to the rubber used. The invention also provides a process for the production of the rubber compounds according to the invention, which is characterised in that the rubber or the blend of rubbers and the carbon black having organic groups according to the invention are mixed in a mixer. Mixing of the rubbers with the carbon black having organic groups according to the invention, optionally rubber auxiliary substances and organosilanes can be performed in conventional mixers, such as rolls, internal mixers and compounding extruders. Such rubber compounds can conventionally be produced in internal mixers, the rubbers, the filler and the rubber auxiliary substances being first mixed together in one or more successive thermomechanical mixing stages at 100 to 170°C. The sequence and time of addition of the individual components can have a decisive influence on the properties of the compound obtained. The crosslinking chemicals can conventionally be added to the rubber compound thus obtained in an internal mixer or on a roll at 40-110°C and the compound processed into the so- called raw compound for the subsequent processing steps, such as moulding and vulcanisation, for example. Vulcanisation of the rubber compounds according to the invention can take place at temperatures of 80 to 200°C, preferably 130 to 180°C, optionally under a pressure of 10 to 200 bar. The rubber compounds according to the invention can be used for the production of moulded articles, for example for the production of pneumatic tyres, tyre treads, cable sheaths, tubes, drive belts, conveyor belts, roll coverings, tyres, shoe soles, sealing rings, profiles and damping elements. The invention also provides moulded articles obtainable from the rubber compound according to the invention by vulcanisation. The rubber compounds according to the invention have the advantage that the dynamic rigidity is the same or higher (equal or better handling properties) and at the same time the loss factor at 60°C (hysteresis) is reduced (lower rolling resistance) in comparison to a rubber compound containing the unmodified starting carbon black. Example 1: Production of the carbon black having organic groups according to the invention by reacting N-(4- thiocyanatophenyl) maleic acid amide with carbon black in a dry mix. 500 g of carbon black N 220 and 100 g of N-(4- thiocyanatophenyl) maleic acid amide are mixed for 5 minutes in a mixer and then conditioned for 5 hours in a muffle furnace at 180°C. On completion of conditioning the carbon black, in ten portions, is suspended in 1 1 of acetone per portion, extracted, washed with acetone and dried. After the reaction the product is pulverised by grinding. Conversion: 70% (relative to the N-(4-thiocyanatophenyl) maleic acid amide used) Example 2: Production of the carbon black having organic groups according to the invention by reacting N-(4- thiocyanatophenyl) maleic acid amide with carbon black in solution 500 g of carbon black N 220 are suspended in a solution of 34 g of maleic acid amide of 4-thiocyanatoaniline in 10 1 of acetone. The solvent is then removed by distillation. The remaining carbon black-reagent blend is conditioned for 5 hours in a muffle furnace at 180°C. On completion of conditioning the carbon black, in ten portions, is suspended in 1 1 of acetone per portion, extracted, washed with acetone and dried. After the reaction the product is pulverised by grinding. Conversion: 82% (relative to the N-(4-thiocyanatophenyl) maleic acid amide used) Example 3: Production of the carbon black having organic groups according to the invention by reacting N-(4- thiocyanatophenyl) maleic acid amide with carbon black in solution 500 g of carbon black N 220 are suspended in a solution of 67 g of maleic acid amide of 4-thiocyanatoaniline in 10 1 of acetone. The solvent is then removed by distillation. The remaining carbon black-reagent blend is conditioned for 5 hours in a muffle furnace at 180CC. On completion of conditioning the carbon black, in ten portions, is suspended in 1 1 of acetone per portion, extracted, washed with acetone and dried. After the reaction the product is pulverised by grinding. Conversion: 87% (relative to the N-(4-thiocyanatophenyl) maleic acid amide used) Example 4: Production of the carbon black having organic groups according to the invention by reacting N-(4- thiocyanatophenyl) maleic acid amide with carbon black in solution 500 g of carbon black N 220 are suspended in a solution of 100 g of maleic acid amide of 4-thiocyanatoaniline in 10 1 of acetone. The solvent is then removed by distillation. The remaining carbon black-reagent blend is conditioned for 5 hours in a muffle furnace at 180°C. On completion of conditioning the carbon black, in ten portions, is suspended in 1 1 of acetone per portion, extracted, washed with acetone and dried. After the reaction the product is pulverised by grinding. Conversion: 70 % (relative to the N-(4-thiocyanatophenyl) maleic acid amide used) Comparative example 1: Production of OH-surface-modified carbon black in solution according to DE 10012783 500 g of carbon black N 220 are suspended in a solution of 100 g of maleic acid amide of 4-hydroxyaniline in 10 1 of acetone. The solvent is then removed by distillation. The remaining carbon black-reagent blend is conditioned for 5 hours in a muffle furnace at 180°C. On completion of conditioning the carbon black, in ten portions, is suspended in 1 1 of acetone per portion, extracted, washed with acetone and dried. After the reaction the product is pulverised by grinding. Conversion: 70 % Comparative example 2: Production of surface-modified carbon black by reacting N- (4-sulfamoylphenyl) maleic acid amide with carbon black according to DE 10012783 in a dry mix 500 g of N 220 and 70 g of N-(4-sulfamoylphenyl) maleic acid amide are mixed in a mixer for 5 minutes and then conditioned for 5 hours at 180°C. After the reaction the product is pulverised by grinding. Conversion: (relative to the N-(4-sulfamoylphenyl) maleic acid amide used) 59 % Example 5: Rubber compounds The formulation used for the rubber compounds is shown in Table 1. The unit phr denotes parts by weight relative to 100 parts of the crude rubber used. The general process for the production of rubber compounds and vulcanisates thereof is described in the following book: "Rubber Technology Handbook", W. Hofmann, Hanser Verlag 1994. The polymer Buna SBR 1500 is an emulsion-polymerised SBR copolymer from Buna SOW Leuna Olefinverbund GmbH having a styrene content of 23.5 % and a viscosity ML(1+4) 100°C of 50. Edenor ST1 GS from Caldic Deutschland GmbH is used as stearic acid and Protektor G3108 is a wax produced by Paramelt B.V.. Vulkacit CZ (CBS) is a commercial product from Bayer AG. Carbon black NT 220 is an ASTM carbon black and is produced by Degussa AG as Corax N 220. The rubber compounds are produced in an internal mixer according to the mixing instructions in Table 2. The rubber compound according to the invention displays a markedly higher Dmax-Dmin value in comparison to the reference blends. Whilst the rubber compound according to the invention has a comparable modulus level at 300% elongation, the modulus at 100% elongation is markedly higher in comparison to the reference blends. This then also explains the higher dynamic rigidity E*. The tan8 60°C value is reduced in the rubber compound according to the invention (improved rolling resistance). The effect becomes even clearer in RPA measurement (Figures 1 to 4). Whilst the comparative blends and the blend according to the invention display identical behaviour in the raw compound (Table 5), in terms of both G* (Figure 1) and tan8 (Figure 2), the behaviour changes after vulcanisation (Figures 3 + 4 / Table 6). In the vulcanisate the rubber compounds according to the invention are characterised in that they have a higher Payne effect and a lower tanδ value with small deflections. Description of the RPA test method: The RPA data is measured with a rubber process analyser (RPA) supplied by alpha-technologies (deformation type: shear torsion, temperature: 60°C, frequency: 1.6 Hz, dynamic shear amplitude: 0.28% - 42%, 15 measuring points in ascending order distributed equidistantly along the logarithmic scale of shear amplitude). Plotting the dynamic shear modulus as a function of amplitude in the above amplitude range describes the Payne effect. The measuring principle is described in J. Frohlich and H.D. Luginsland, Rubber World, Vol. 224, No. 1, p.28ff. Procedure: The amplitude sweep defined above is applied to a raw compound sample from the last productive step in each case in the RPA at 60°C. The dynamic modulus G*RC and the loss factor tanSRC as a function of the shear amplitude are obtained as the measurement results. The actual Payne effect can be calculated as delta G*RC := G*[email protected]% - G*RC@42%. G*RC and tan8RC at various amplitudes between 0.28% and 42% and delta_G*RC represent the RPA data for the raw compound. In an additional measurement, a new raw compound sample from the last productive step in each case is first vulcanised in the RPA at a vulcanisation temperature T_vulc for a vulcanisation time of t_vulc. Immediately thereafter, the sample vulcanised in this way is cooled in the RPA without opening the measuring chamber with the aid of compressed air (room temperature) until the measuring temperature of 60oC has been reached and stabilised. Depending on the vulcanisation temperature and the sample used, this process takes a few minutes - typically around 2 to 5 minutes - and is performed automatically by the RPA. Immediately thereafter, without opening the measuring chamber in the meantime, an amplitude sweep as defined above is applied to this vulcanised sample in the RPA at 60°C. The dynamic modulus G*v and the loss factor tanδv as a function of the shear amplitude are obtained as the measuring results. The actual Payne effect can then be calculated as delta G*v := G*[email protected]% - G*v@42%. G*v and tanSv at various amplitudes between 0.28% and 42% and delta_G*v then represent the RPA data for the vulcanisate. Example 6: Rubber compounds The formulation used for the rubber compounds is shown in Table 7. The rubber compounds according to the invention display a markedly higher Dmax-Dmin value, modulus at low elongations and dynamic modulus (E* 60°C) in comparison to the reference blend. The tanδ 60°C is reduced (lower rolling resistance) in comparison to the reference blend. Example 7: Rubber compounds The formulation used for the rubber compounds is shown in Table 10. The polymer VSL 5025-1 is a solution-polymerised SBR copolymer from Bayer AG with a styrene content of 25 wt.% and a butadiene content of 75 wt.%. The copolymer contains 37.5 phr oil and has a Mooney viscosity (ML l+4/100°C) of 50 ±4. The polymer Buna CB 24 is a cis-1,4-polybutadiene (neodymium type) from Bayer AG with a cis-1,4 content of 97 %, a trans-1,4 content of 2 % and a 1,2-content of 1 %. Naftolen ZD from Chemetall is used as aromatic oil; Vulkanox 4020 is a 6PPD from Bayer AG. The rubber compounds according to the invention display a markedly higher Dmax-Dmin value, dynamic modulus (E* 60°C) and a higher or equal modulus, at low elongations in comparison to the reference blend. The tanδ 60°C is reduced (lower rolling resistance) in comparison to the reference blend. Example 8: Rubber compounds The formulation used for the rubber compounds is shown in Table 13. The natural rubber is an SMR 10 (from Malaysia, ML(1+4) 100°C = 60-70). Vulkanox HS/LG is a TMQ from Rhein-Chemie GmbH Mannheim. Rhenogran TBBS-80 is an 80 % N-tert.-butyl-2-benzothiazole sulfenamide accelerator from Rhein-Chemie GmbH Mannheim. The rubber compounds are produced in an internal mixer according to the mixing instructions in Table 14. The rubber compounds according to the invention display a markedly higher Dmax-Dmin value, dynamic modulus (E* 60°C) and modulus at low elongations in comparison to the reference blend. The tanδ 60°C is reduced (lower rolling resistance) in comparison to the reference blend. WE CLAIM: 1. A carbon black having attached thereto at least one organic group selected from the group consisting of an N-(4-thiocyanate alkyl)succinimide, N-(4-thiocyanate aryl)succinimide, N-(4-thiocyanate alkyl)amide and N-(4-thiocyanate aryl)amide group. 2. Carbon black having organic groups as claimed in claim 1, wherein the organic group an N-(4-thiocyanate alkyl)succinimide, N-(4- thiocyanate aryl)succinimide, N-(4-thiocyanate alkyl)amide or N-(4- thiocyanate aryl)amide group. 3. Carbon black having organic groups as claimed in claim 1, wherein the organic group is an N-(4-thiocyanatophenyl) succinimide or N-(4- thiocyanatophenyl)amide group. 4. A process for the production of a carbon black as claimed in claim 1, comprising reacting carbon black with an organic compound containing an organic group which is a member selected from the group consisting of an N-(4-thiocyanate alkyl)succinimide, N-(4-thiocyanate aryl)succinimide, N-(4-thiocyanate alkyl)amide and N-(4-thiocyanate aryl)amide group. 5. Process for the production of a carbon black as claimed in claim 1, wherein the carbon black is reacted with a diazonium salt and the diazonium salt contains a thiocyanate group. 6. Rubber compound, wherein it contains a rubber or a blend of rubbers and a carbon black having organic groups as claimed in claim 1. 7. Rubber compounds as claimed in claim 6, wherein the carbon black having organic groups is used in a quantity of 10 to 150 parts by weight, the parts by weight relating to 100 parts by weight of rubber. 8. Process for the production of rubber compounds as claimed in claim 6, wherein the rubber or the blend of rubbers and the carbon black with organic groups are mixed in a mixer. 9. Rubber compound as claimed in claim 6, wherein the dynamic rigidity and the loss factor tan8 at 60°C are improved in comparison to a rubber compound containing the unmodified starting carbon black. ABSTRACT Title: Carbon black A carbon black having attached thereto at least one organic group selected from the group consisting of an N-(4-thiocyanate alkyl)succinimide, N-(4- thiocyanate aryl) succinimide, N-(4-thiocyanate alkyl)amide and N-(4- thiocyanate aryl)amide group.

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