MXPA97007091A - Polyethylene glycol treated carbon black and compounds thereof - Google Patents

Abstract

A treated carbon black may be produced by treating carbon black with at least one polyethylene glycol having a molecular weight of from about 1,000 to about 1,000,000. The treated carbon black may be used in forming polymeric compositions, such as semi-conductive and insulating compounds, for example for use in electrical cables.

Description

BLACK OF CARBON TREATED WITH POLYETHYLENE GLYCOL AND COMPOUNDS OF THE SAME BACKGROUND OF THE INVENTION This invention relates to treated carbon black, suitable for use as compositions _ ^ _ ^ _ B ^ _ semiconductors such as in electric cables. More particularly, the present invention relates to carbon black treated with a polyethylene glycol, also known as a homopolymer of ethylene oxide, and semiconductor compositions including, for example, a polyolefin and the treated carbon black. Such treated carbon blacks are free flowing, produce low levels of dust, are resistant to wear by rubbing, are easily dispersible in polymeric systems and provide improved rheological, mechanical and electrical properties. The present invention also relates to a process for the production of such treated carbon blacks, and the compositions produced therefrom. Any of a wide variety of carbon blacks may be used in the present invention. In this way, the term black carbon is used in present in its generic sense to include types of REF: 25601 coal finely diviatWos such as carbon for arc lamp, channel black, furnace black, acetylene ~ black and the like. Preferably, the carbon black is in a soft form. Although 5 carbon blacks are easily dispersed in liquid and polymeric systems in their soft forms, these are extremely difficult to "handle with respect to precise transfer and weighing. * • particularly due to its low apparent densities 10 and in general to high dust levels, which tend to lead to compaction and consequent irregular feeding in continuous composition operations. Such effects are undesirable because, for example, continuous composition operations are desirable for wire and cable composites as a means to ensure uniformity and cleanliness of the compounds. A persistent problem with carbon black has been the relative difficulty and inconvenience associated with the manufacture, transportation and use of carbon black. When carbon black is packaged, transported and removed from its packaging, carbon black powder is produced. To improve the handling characteristics of soft carbon blacks, they are agglomerated into.

General cold by various mechanical processes to produce pellets, either in the dry state or with the help of a liquid auxiliary for the formation of pellets. In general, carbon black particles are held together by weak forces. The most common process is to convert soft carbon blacks into pellets using a granulation aid # Liquid such as oil or water. However, it has been found that the agglomeration or densification process has a damaging effect on the dispersion characteristics of soft carbon blacks. That is, as soft carbon blacks are agglomerated into pellets, they become less readily dispersible in polymer systems. 15 Therefore, there is a relationship between acceptable handling characteristics and ease of dispersion. In order to compound the well-dispersed formulations with these carbon blacks, these are often granulated with materials such as sodium lignosulfonate, water, sucrose, etc., as described below. However, granulation auxiliaries often produce less than adequate results, or result in carbon black which is incompatible with the formulation in which it is to be combined. For example, some carbon blacks do not develop adequate resistance from pellets or granules when granulated with water. This is due to the van der Waals forces existing between the carbon structure. In this wayAlthough they are in the form of pellets, they are very friable and result in high levels of dust. The result is inconsistent feeding and consequent nonhomogeneous dispersion in a compound. The processes for the granulation of blacks, "carbon to produce carbon black pellets, are known in the art. For example, U.S. Patent No. 2,065,371 to Glaxner, discloses a wet granulation process whereby the soft carbon black and a liquid such as water are &; combined and agitated until spherical pellets of carbon black are formed. The spheres are then dried to reduce the water content to less than 1%, to form carbon black pellets. In addition to water, it is known that a wide variety of binder additives are useful in the wet granulation process to further improve the handling characteristics of the pellets of soft carbon blacks. For example, the following 25 references describe the use of various binding additives such as granulation aid to produce carbon blacks: US Patent No. 2,427,238 to Swart de-scribes the use of a number of liquids or hygroscopic organic solutions, including ethylene glycol, in the composition of rubber-like materials. U.S. Patent No. 2,850,403 to Day discloses the use of carbohydrates such as sugar, molasses, soluble starches, saccharides and lignin derivatives as additives "binders for granulation in the range of 0.1% to 0.4% by weight of the dry carbon black. The wet pellets are then dried for a given residence time at a temperature of 150 ° C to 425 ° C to carbonize the carbohydrate binder. The North American Patent No. 2,908,586 to Braendle et al. Discloses the use of a turpentine resin emulsion as an alternative for carbohydrates, in a preferred amount of 0.5% to 2.0% by weight of the dry carbon black. The North American Patent No. 2,639,225 to Venuto describes the use of anionic sulfonate and sulfate surfactants as granulation aids in an amount of 0.1% to 0.5% by weight of the dry carbon black. U.S. Patent No. 3,565,658 to Frazier et al. Describes the use of a non-surfactant fatty amine ethoxylate ionic as a granulation aid, wherein AI fatty amine ethoxylate has an ethoxylation level in the range of 2 to 50 moles of ethylene oxide per fatty amine group. The nonionic surfactant is described as being preferably present in the range of 0.05% to 5.0%. Similarly, US Patent No. 3,645,765 also to Frazier et al. Describes the use of a non-ionic surfactant of fatty acid ethoxylate or of rosin resin acid in the range of 0.1% to 10.0% by weight of black carbon. The non-ionic surfactant is described as having an ethoxylation level of 5.0 to 15.0 moles of ethylene per acid group. Soviet Patent Publication No. 937,492 discloses the use of an aqueous solution at 0.1% -5.0% of a reaction product of urea and an ethoxylated alkylolamide, where the level of ethoxylation is from 1.0 to 7.0 moles of sodium oxide. ethylene by alkylolamide. Finally, U.S. Patent No. 3,844,809 to Murray describes the use of a nonionic surfactant containing poly (ethylene oxide) and poly (dimethyl silicone) groups that are randomly repeated. The reference discloses that 0.4% to 2.5% of an aqueous solution containing 0.001% to 0.1% of the nonionic surfactant, results in a reduction in pellet powder levels. Molasses are also included at substantially higher concentrations of up to 2.0% as a co-agglomerator, and nitric acid is included in an amount of up to 15.0% as a source of oxidation. The above patents disclose improved qualities for pellet handling, but do not disclose changes in the performance properties of granular carbon black in final product applications. Among the handling characteristics of carbon black that can be improved by the additives, binders, and the level of such additives being used in the granulation process, are characteristics such as adhesion, dispersion capacity, dispersion speed, Stability of viscosity and antistatic properties. For example, Japanese Patent Publication No. 01-201,369 describes the use of an amphoteric carboxylic acid type surfactant at a concentration of 0.001% to 0.1% in the granulation water, to produce carbon black pellets with low adhesion and excellent dispersion capacity. U.S. Patent No. 3,014,810 to Dybals i et al. Describes the benefits of wet granulation of a range of pigments, including carbon black, with 0.05% to 5% by weight of a mixture of a quaternary ammonium compound and a * 8 < & E * -bis (2-hydroxyethyl) alkyl amine. The benefits described include improvements in dispersion speed, viscosity stability and antistatic properties. As described above, oil has also been used, with or without the inclusion of water, as a granulation aid. For example, # US Patents Nos. 2,635,057 to Jordan, 3,011,902 to Jordan and 4,102,967 to Vanderveen and collaborators describe the use of oil, such as mineral oil, in the granulation process to improve the handling characteristics of the carbon black pellets. In addition, the use of polymers in an emulsion, organic solvent, solution or molten form has has been described as a means for modifying the properties of carbon black pellets, for example as described in U.S. Patent Nos. 2,511,901 to Bunn (latex emulsions), 2,457,962 to Whaley (aqueous emulsions or rubber dispersions), 4,440,807 to Gunnell (molten rubber or a rubber solution or emulsion), 4,569,834 to West et al. (Emulsion of an oxidized polyethylene) and 5,168,012 to Watson et al. (A rubber latex) and in the Japanese Patent Publication No. 77-130,481.

Other alternative granulation auxiliaries for producing carbon black pellets include sodium lignosulfonates, silanes, sucrose and nonionic dispersants such as alkyl succinimides and 5 alkylated succinic ethers. However, such alternatives have not produced favorable carbon black pellets and / or polymeric compositions. By For example, carbon blacks produced using sodium lignosulfonates are generally described as unsuitable for use in polymer compositions, (semiconductors due to the increased propensity for the formation of water branches resulting from the increased sulfur content. disadvantages of alternative aids for granulation 15 include the adhesion of carbon blacks to the equipment IB for processing, the difficulty in the application of granulation aids to carbon blacks, and (particularly in wire and cable formulations) the formation of water branches in polymeric compositions. The use of polyethylene glycol in the production of rubber and thermoplastic resin materials is also generally known. For example, U.S. Patent No. 4,230,501 to Howard et al. 25 describes the use of polyethylene glycol in a pigment concentrate that is in plastics. The polyethylene glycol hydrocarbon is incorporated as an additive for the control of the viscosity in a natural or synthetic wax, which is then mixed with 51% to 85% by weight of a pigment, to form a pigment concentrate. U.S. Patent No. 4,397,652 to Neumann describes the production of powders containing organic dyes and optical brighteners, which produce non negligible dust levels. He; Polyethylene glycol is described as an adhesive component, at molecular weights greater than 3,000, and as a powder binding agent, at molecular weights between 200 and 1,000. British Patent Specification No. GB-975,847 describes the use of an aqueous solution of polyethylene glycol or an aliphatic derivative as a means to produce agglomerates of organic rubber chemicals. The pellets of the composition are formed via an extrusion process, and subsequently dry at low temperatures. Polyethylene glycol is also known in the art as an additive for direct composition in crosslinked and thermoplastic resin compositions. For example, U.S. Patent No. 4,013,622 a DeJuneas et al. Describes the incorporation of 100 to 600 ppm of polyethylene glycol, which has a molecular weight of 600 to 20,000 in a greater amount of low density polyethylene. Polyethylene glycol is incorporated into the thermoplastic resin to reduce the breakdown of polyethylene glycol during blown film operations. As a further example, U.S. Patent No. 3,361,702 to artman et al. Describes the use of polyethylene glycol or branched ethoxylate molecules as plasticizers. for the ethylene-acrylic acid copolymers. It is also known that polyethylene glycol is useful in the production of polymer compositions. For example, US Patents Nos. 4,812,505 to Topcik, 4,440,671 to Turbett and 4,305,849 to Kawasaki and collaborators describe the use of polyethylene glycol, which has a molecular weight of 1,000 to 20,000, to reduce the branching characteristics of water in polymeric compositions for electrical insulation materials. The North American Patent No.

No. 4,812,505 to To cik describes the incorporation of 0.1 to 20% by weight of polyethylene glycol in a polymeric composition. U.S. Patent No. 4,440,671 to Turbett discloses the incorporation from about 0.2 to about 1 part of polyethylene glycol, Having a molecular weight of 1,000 to 20,000 per part by weight of diphenylamma. U.S. Patent No. 4,305,849 to Kawasaki et al. Describes the incorporation of between 0.3% and 10% by weight of polyethylene glycol directly into an insulating polymer composition by kneading the polyethylene glycol with the polymer. In this regard, the formation of water branches refers to a phenomenon that occurs when a polymeric insulation material such as polyolefin 10 is subjected to an electric field over a prolonged period of time in a water-containing environment. This phenomenon will be distinguished from branched electrical discharges (carbonization of the insulation material due to electric discharges) and to the 15 chemical branches (crystals formed from reactive gases on the surface of the conductor). The reduction of the water branching phenomenon is also addressed in U.S. Patent No. 4,612,139 to Kawasaki et al, which is aimed at reducing the problem of water branching in semiconducting polymeric compositions containing carbon black. The patent discloses that polyethylene glycol can be directly incorporated into a semiconductor polymer composition to eliminate the phenomenon of water branching. The polyethylene glycol, which has a molecular weight of 1,000 to 20,000 is incorporated into the polymer in an amount from 0.1% to 20% by weight of the polymer. Similar compositions are described in German Patent No. DE 23 23 488. The German Patent discloses that polyethylene glycol and other mobile additives are beneficial in reducing interlaminar adhesion between the insulating layer and the outer conductive layer (e.g., insulation shielding). ) in a cable construction electric. Japanese Patent Publication Nos. 61-181,859 and 61-181,860 describe electroconductive compositions. The compositions comprise a crystalline polyalkylene oxide and carbon black or graphite. Patent No. 61-181,859 also discloses that the polymer is modified to contain carboxyl or carboxylic acid side chains.

BRIEF DESCRIPTION OF THE INVENTION There remains a need for improved granulation aids, for use in the production of carbon black pellets, where the handling characteristics of the pellets are improved. pellets and the operating characteristics of the polymeric compositions in which granulation aid, produces treated black carbon pellets < 3j8 © have such improved handling and operation characteristics. There also continues to be a need for improved compositions for the production of articles such as wire and electric cable. Specifically,. there continues to be a need for materials with improved performance characteristics. It has been discovered that the treated carbon black, mentioned above, can be used for producing polymer compositions, such as semiconductor and insulating polyolefin compositions, having such improved performance characteristics. Such compositions of treated black carbon and improved polymers, which contain the carbon black treated with unique and novel properties, and processes for the production thereof, are provided herein. Specifically, the present invention provides polymeric compositions, such as a . semiconductor composition comprising a polyolefin copolymer, copolymer, or terpolymer, and a carbon black treated with at least one polyethylene glycol having a molecular weight of from about 1,000 to about 1,000,000. The present invention also provides granular carbon black wherein the carbon black pellet comprises carbon black treated with at least one polyethylene glycol having a molecular weight from about 1,000 to about 1,000,000. The present invention further provides a process for preparing such carbon black pellets, comprising the treatment of a carbon black with at least one polyethylene glycol having a molecular weight of from about 1,000 to about 1,000,000, to produce the treated carbon black . The polymer compositions incorporating the treated carbon blacks of the present invention can, for example, be used as semiconductor layers bonded to primary insulation layers or electrical conductors, such as in electrical cables. For example, the polymeric compositions can be used as insulation shielding materials in the form of semiconductor layers that m ^ j ___._ »__ > _____! «_____ * __ & '_.....

They can be easily torn off or removed from the insulation materials. These carbon blacks can also be used in the filler compounds in strands, either conductive or non-conductive, or in liner formulations for conductive or non-conductive cables. In addition, these treated carbon blacks can be incorporated in smaller amounts, without imparting semiconductor properties to the composition, for example as a colorant in the insulating compounds.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an illustration of a typical power cable.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES Any of a number of carbon blacks can be used in the present invention, including finely divided carbon black as carbon for arc lamp, furnace carbon, and the like. Preferably, the carbon black is in the soft form.

In the processes of the present invention, the carbon black, preferably in the soft form, is treated with a polyethylene glycol having a molecular weight of from about 1,000 to about 1,000,000,000. In the present specification, polyethylene glycol is referred to as a "polyethylene glycol compound" or simply as "polyethylene glycol".

However, it is understood that the terminology also includes those polyethylene glycol compounds which are also referred to as ethylene oxide homopolymers, and include compounds such as those resulting from the condensation polymerization of ethylene glycol, and addition polymerization. ethylene oxide. The term "polyethylene glycol compounds" encompasses in this way those polymers having the repeating unit (CH 2 CH 20) n. The polyethylene glycol compound can be added onto the carbon black as a granulation aid during the formation of the carbon black pellets. In the present invention, it is preferred that the polyethylene glycol has a molecular weight of from about 1,000 to about 1,000,000. More preferably, the polyethylene glycol has a molecular weight of from about 20,000 (preferably greater than 20,000) to about 1,000,000 and still more preferably from about 35,000 to about OD,). In the present invention, it is preferred that the polyethylene glycol compound be present in an amount of from about 0.1% to about 50% by weight of the carbon black. That is, with the polyethylene glycol compound which is used as a granulation aid on the carbon black pellets, it is preferred that the compound of The polyethylene glycol is present in the treated carbon black in an amount from about 0.1% to about 50% by weight. More preferably, the polyethylene glycol compound may be present in an amount of about 0.1% up to about 20%, and even more preferably in an amount of about 1% to about 10% by weight of carbon black. In the preparation of treated carbon blacks, it may be preferable to form a solution containing the polyethylene glycol compound. If a solution of the polyethylene glycol compound is used, the solvent can be any of a wide variety of solvents capable of dissolving the polyethylene glycol compound. For example, the polyethylene glycol compound can be Easily dissolved in water and / or in a variety of organic solvents including, but not limited to "methanol, ethanol, isopropanol, carbon tetrachloride, trichlorethylene, benzene, toluene, xylene, acetone, mixtures thereof and the like. For the solvent, it is more important that the polyethylene glycol compound is homogeneously dispersed or dissolved in the solvent, but the exact solvent used is not generally crucial. Preferably, however, the polyethylene glycol compound is used in an aqueous solution, especially as the molecular weight of the polyethylene glycol compound is increased. Based on the present disclosure, one skilled in the art will be able to easily select a suitable solvent for the specific application. Alternatively, the polyethylene glycol compound can be heated to a temperature above the melting point of the compound, where the viscosity of the molten compound is such as to facilitate spray application on the carbon black. Here, it is noted that many of the polyethylene glycol compounds are soluble in water at room temperature, and therefore little or no heating may be required. The viscosity of the molten compound, although not limiting, is preferably below about 10 poises. The black temperature of Polyethylene glycol must be maintained above the melting point of the compound, for a sufficient time gf & Allow homogeneous mixing. In the embodiments of the present invention, the polyethylene glycol compound is used as a granulation aid to form carbon black pellets from carbon blacks. The granulation process generally comprises contacting the carbon black with a solution containing the polyethylene glycol compound and optionally selecting the heating and drying of the carbon black pellets. The carbon black may be contacted with the polyethylene glycol compound by introducing the carbon black into a granulator apparatus, with the polyethylene glycol compound. For example, carbon black, preferably in the soft form, can be introduced into the granulator with a solution of the polyethylene glycol compound. Examples of such granulation apparatus are known in the art, and include spike granulators. When the polyethylene glycol compound is introduced into the granulator apparatus in the form of a solution, for example in any of the solvents described above, the concentration of the polyethylene glycol compound in the solvent is preferably in the range of about 0.5% to about 35%. % in weigh. However, the concentration of the polyethylene glycol compound in the solvent, and the relative amount of the solvent to the carbon black, must be adjusted to ensure that the appropriate amount of the compound is present. # polyethylene glycol on the black particles of carbon, as described above. After the carbon black has been contacted with the polyethylene glycol compound, the resultant wet carbon black pellets can optionally be heated to a temperature controlled and for a controlled period of time and / or reduced pressure to dry the pellets. The treated carbon black of the present invention can be used to form a wide variety of compositions. For example, black The treated coal can be used in the formation of pigment materials, or it can be combined with polymers and other optional components to form semiconductor and insulator compositions, such as for use in electrical cables and electrical shielding.

The semiconducting compositions can be made by combining a polymer with a number of semiconductor-like materials, insulating materials can be formed by incorporating smaller amounts of carbon black, for example as a dye, into a polymeric composition. Such insulating materials can be formed by the combination of a polymer and a quantity of black of - coal much smaller than enough to impart semiconducting properties to the material. Specifically, the polymer compositions in the embodiments of the present invention can be made by combining a polymer such as a polyolefin with a quantity of carbon black sufficient to make semiconductors to the compositions. In the preparation of the polymeric compositions of the present invention, the polymer can be selected from any of several homopolymers, copolymers and terpolymers known in the art, the selection being based on the ultimate desired use of the polymer composition. For example, the polymers used in the polymer compositions of the present invention may include, but are not limited to homopolymers, copolymers and polymers of ethylene graft, where the comonomers are selected from butene, hexene, propene, octene, vinyl acetate, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, maleic anhydride, maleic esters of maleic anhydride, carbon and the like; the selected elastomers of natural rubber, polybutadiene, polyisoprene, random styrene-butadiene rubber, polychloroprene, rubber * nitrile, copolymers and ethylene-propylene terpolymers 10 and the like; styrene-homopolymers and copolymers, "including radial and linear polymers of styrene-butadiene, styrene-butadiene-styrene, acrylonitrile-butadiene-styrene, styrene-acrylonitrile and the like; linear and 15 branched polyether or polyester polyols; polyesters and crystalline and amorphous polyamides; alkyd resins, turpentine resin acids or turpentine resin esters; hydrocarbon resins produced from thermal or Friedal Crafts polymerization of cyclic diene monomers such as dicyclopentadiene, indene, eumeno and the like; ethylene / silane copolymers; ethylene / α-olefin-diene terpolymers such as ethylene / propylene / 1,4-hexadiene, ethylene / 1-butene / 1, 4-hexadiene and the like; and hydrocarbon oils such as paraffin oil, naphthalene oil, oil * _ Jt tJM ?? kMa * ** - ^^ Naphthenic hydrogenated and similar; mixtures thereof and the like. In addition, the polymer used in the compositions of the present invention may include copolymers and terpolymers containing the polymers previously identified as major components of the copolymer or terpolymer. Preferably, the polymer used in the compositions of the present invention includes ethylene-vinyl acetate, ethylene-butene such as ethylene / 1-butene, ethylene-octene, ethylene-ethyl acrylate, ethylene-acrylic acid, equivalents these, mixtures thereof and the like. The precise monomer content of the polymers used in the present invention will depend on factors such as economic considerations and the desired applications of the resulting composition. In the case of the use of a polyolefin in the formation of the polymer composition, typically the polymers used in the compositions of the present invention will generally be in the range of about 25 mole percent to about 98 mole percent ethylene, based on the total moles of monomer. Preferably, the polyolefin polymers comprise from about 30 mole percent to about _ia_¿_? i_Aá _______ aa_fe_8_a 95 percent mol, and more preferably from about 35 mol percent to about 90 mol percent ethylene. The other monomers, in the case of the polyolefin copolymers, will comprise the remainder of the polymer. However, the ethylene content in the polymers may vary depending on the comonomer (s) present in the polymer. For example, in the case of an ethylene / vinyl acetate copolymer, It is preferred that the polymer comprises from about 15 mole percent to about 80 mole percent vinyl acetate. Preferably, the ethylene / vinyl acetate copolymer is of the rubber variety, and accordingly has a vinyl acetate content above about 28 mol percent. Still more preferably, the ethylene / vinyl acetate copolymer comprises from about 40 mole percent to about 60 mole percent acetate vinyl. In addition, the polymer, copolymer or terpolymer used in the polymeric formulations of the present invention can be either crosslinked or non-crosslinked. If the polymer is going to be crosslinked, can be added to the formulation any of a wide variety of cross-linking agents such as those known ep, the art. For the typical formulation of a polimépca composition for use in applications of wire and semiconductor wire of the present invention, preferably comprises: 25-55% by weight of a carbon black treated with 0.5 to 10 parts of a polyethylene glycol per * 100 parts of carbon black; 10 0-2% by weight of a stabilizer or antioxidant; 0-5% by weight of an organic peroxide such as dicumyl peroxide; 0-10% by weight of a vinyl silane; and the remainder is a polymer or a mixture of polymers. The formulation may also include an additive polymer such as, for example, acrylonitrile-butadiene elastomer containing, for example, 25-20 wt% acrylonitrile. In the compositions of the present invention, the treated carbon black is generally present in the composition in the amount of from about 0.1 to about 65% by weight, and preferably from about 10 to about 50% by weight, based on the weight of the total composition. Such compositions generally have semiconductor properties. The content of the treated carbon black can, of course, be adjusted according to the desired use of the final composition and the desired relative conductivity of the composition. For example, carbon black can be incorporated into a polymer composition in smaller amounts to provide colorful insulating materials or to improve the ultraviolet light resistance of the compounds. The compositions of the present invention may also include additives appropriate for their known purposes and in known and effective amounts. For example, the compositions of the present invention they may also include additives such as crosslinking agents, vulcanizing agents, stabilizers, pigments, colorants, metal deactivators, oil extenders, lubricants, inorganic fillers and solvents. For example, the polymeric compositions of the present invention can include at least one crosslinking agent, preferably in an amount of from about 0.5 to about 5% by weight, based on the weight of the specific polymer that is tiggíigj t¡__ a¿ fr_ * É _? ___ «s_¿_á * F_S,% í use. An organic peroxide is preferably used as a generator? free radicals and crosslinking agent. Useful organic peroxide crosslinking agents include, but are not limited to a, aβ-bis (tert-butylperoxy) -diisopropylbenzene, dicumyl peroxide, di (tert-butyl) peroxide, and, 5-dimethyl-2,5-di (tert-butylperoxy) -hexane. Various other known coagents and crosslinking agents can also be used. For example, "organic" peroxide crosslinking agents are described in U.S. Patent No. 3,296,189, the full disclosure of which is incorporated by reference herein. As examples of antioxidants and processing aids that can be incorporated into the polymer compositions of the present invention, there may be mentioned, for example, 1,2-dihydro-2,2,4-trimethylquinoline, 3,5-diter-but-yl? octadecyl-4-hydroxyhydrocinnamate, 4,4'-thio-bis- (3-methyl-6-tert-butylphenol), thio-diethylene-bis- (3,5-ditert-butyl-4-hydroxyl), thio Distearyl dipropionate, polymerized, mixtures thereof and the like. Such antioxidants may be present in compositions of the present invention in an amount preferably from about 0.4 to about 2.0% by weight, and more preferably from about 0.4 to about 0.75% by weight. Other antioxidants used in the compositions of the present invention include spherically hindered phenols, phosphites and selected amines. In addition, processing aids can be added to the polymer formulations for their known purposes. Thus, although processing aids are not necessary to achieve homogenous mixtures and reduced viscosity, these can be added in the compositions of the present invention to further improve these properties. For example, processing aids may include, but are not limited to, metal stearates such as zinc stearate and aluminum stearate, stearate salts, stearic acid, polysiloxanes, stearamide, ethylene-bisoleyamide, ethylene-bis-stearone, mixtures of the same and similar. Processing aids, when incorporated into the compositions of the present invention, are generally used in amounts of from about 0.1 to about 5.0 weight percent, based on the total weight of the polymer composition.

The polymeric compositions of the present invention can be manufactured using conventional machinery and methods to produce the desired final polymer product. The compositions can be prepared by batch mixing or continuous mixing processes such as those well known in the art. For example, equipment such as IAB Banbury mixers, Buss co-mixers, and twin screw extruders can be used to mix the ingredients of the formulation. For example, the components of the polymer compositions of the present invention can be blended and pelletized for future use in the manufacture of such materials as insulated electrical conductors. 15 The polymer compositions of the present »__%. invention can be incorporated into any product where the properties of the polymer composition are suitable. For example, polymeric compositions are particularly useful for the preparation of insulated electrical conductors, such as electrical wires and power cables. Depending on the conductivity of the polymer composition, the polymer composition can be used, for example, as a semiconductor material or as a material insulator on such wires and cables. More preferably, a semiconductor shield of the polymer composition can be formed directly on an internal electrical conductor such as a conductor shield, or on an insulating material such as a bonded or detachable insulation shield 5 or as an outer shell material. These carbon blacks in the selected polymer compositions can also be used in strand filling applications, whether they are conductive or non-conductive formulations. 10 For ease of illustration, Figure 1 - describes the typical comments of an electrical cable. Figure 1 shows a typical power cable comprising a conductive core (such as a plurality of conductive wires), surrounded by several protective layers. In addition, the conductive core may contain a filler of strands or filaments with conductive wires, such as a water blocking compound. The protective layers include a liner layer, the insulating layer, and semiconductor shields. When polyethylene glycol is used to treat carbon blacks, a polymer composition containing these treated carbon blacks shows properties that are unique and different from those observed when the polyethylene glycol is mixed directly into the polymer composition. For example, in a polymeric composition comprising a carbon black treated with polyethylene glycol, as compared to a polymer formulation comprising a carbon black and polyethylene glycol directly mixed in the formulation, the differences described below can be observed. Here, these differences are noted for a polymer composition comprising at least one polyolefin resin, an antioxidant, a curing agent, carbon black, and a polyethylene glycol compound either as an additive or as a treatment compound. for carbon black. By directly adding the polyethylene glycol compound to a polymeric formulation the time at 50% cure and 90% cure 15 (tc (50) and tc (90), respectively) is decreased. In addition, the addition *%, direct of the polyethylene glycol compound decreases the surface burn time (ts2) of the polymer composition. By increasing the proportion of the additive of the polyethylene glycol compound, these results are further deteriorated. However, these changes are not observed in a polymeric composition comprising carbon black treated with the polyethylene glycol compound. Curing times and increased surface burn time 25 are preferable, for example, to prevent the product from ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ The volume resistivity of the polymer compositions can also be unexpectedly affected by the use of the polyethylene glycol compound as a treatment compound for carbon black. Specifically, there is an interaction of the level of adhesion of the polyethylene glycol compounds as granulation aids of the carbon black. By increasing the level of the polyethylene glycol compound in the treated carbon black, the volume resistivity of the polymer composition is significantly increased over a wide temperature range in some polymer systems, while the volume resistivity in other polymer systems is decreased. In this way, the effect of volume resistivity is dependent on the resin. By increasing the level of the polyethylene glycol compound used as an auxiliary to the carbon black treatment, these results are further improved. The use of the treated carbon black also affects the viscosity of the extruder during the processing of the polymer compositions. For example, the use of carbon blacks treated in high viscosity polymeric compositions significantly decreases the viscosity of the compositions, while maintaining performance levels. In addition, as the cutting speed is increased during processing, the increased levels of the polyethylene glycol compound in the treated carbon blacks further decrease the viscosity while maintaining the performance levels. These 10 results are superior to the results obtained < by directly adding the polyethylene glycol compound to the formulation, because the decreased viscosity allows for increased yield or constant yield at decreased cutting speeds. In addition, the use of the compound of The polyethylene glycol as a treatment compound for carbon black is observed to significantly decrease the adhesion of the polymer composition to the crosslinked polyethylene. This decreased adhesion is preferable, for example, because it increases the release capacity of the polymer composition of the other compositions to which it is adhered. For example, decreased adhesion in the case of electric cable allows for easier removal ability of the semiconductor shield from an underlying insulating material. Based on the present disclosure, one of skill in the art will recognize that the various components of the polymer compositions discussed above can be selected and adjusted as necessary to achieve specific end products with desirable performance characteristics. The invention will now be described in more detail with reference to preferred embodiments thereof, it being understood that these examples are intended to be illustrative only, and it is not intended that the invention be limited to the materials, conditions, parameters of the invention. process, etc., described herein. All parts and percentages are by weight unless otherwise indicated.

EXAMPLES 20 Example 1 Pellets of carbon black treated with polyethylene glycol are formed, wherein the polyethylene glycol is used as an auxiliary of the JÉÉfrfi r i ^^^^^^^ granulation in the production of carbon black pellets from carbon black in its soft form. In this example, carbon black has an absorption number of dibutyl phthalate (DBP) of 138 cm 100 g and an iodine surface area of 68 mg / g. Here, the DBP is measured according to ASTM D 2414, and the iodine surface area is measured according to ASTM D 1510. The carbon black is combined with an aqueous polyethylene glycol binder solution (molecular weight = 20, 000) sufficient to produce a carbon black, treated having 2% polyethylene glycol by weight of carbon black. The carbon black and the aqueous binder solution are mixed in a continuous pin granulator operating with a rotor speed of 1,100 rpm and a mass flow rate in the range of 544.3 to 816.5 kg / hour (1,200 to 1,800 lbs / hour ). The pellets are then dried in a hot rotating drum to provide carbon black pellets with a moisture content less than about 0.6%. The carbon black pellets produced in this way are evaluated for the resistance of the pellets according to ASTM D 1937. The pellets of carbon black are also evaluated for wear by rubbing the pellets using a version ^^^^^^^^^^^ ¿¿^ ¿¿¿¿¿¿¿¿¿¿¿¿Modified ASTM D 4324, which is modified to generate the level of powder after the agitation of the samples of black pellets of coal for five and twenty minutes. The results of these measurements are presented in Table 1 below.

Examples 2 and 3 Carbon black pellets treated with polyethylene glycol are prepared, as in Example 1, -, except that the molecular weight of the polyethylene glycol contained in the aqueous binder solution is 35,000 (Example 2) and 100,000 (Example 3). The same pellet resistance and pellet wear measurements are performed as in Example 1, and the results are presented in Table 1 below.

Comparative Example 1 Carbon black pellets are prepared according to Example 1, except that the binder solution consists solely of water, for example, it does not contain polyethylene glycol. The same resistance and wear measurements are performed by rubbing the pellets as in Example 1, and the results are presented in Table 1 below.

TABLE 1 Example 4 A semiconductor compound 10 is produced using the carbon black pellets treated with polyethylene glycol produced in Example 1 above. The carbon black pellets are composed of an ethylene vinyl acetate resin using a twin screw extruder ZSK. The ethylene vinyl acetate resin has a melt index of 3 and contains 40% vmyl acetate by weight. The resulting compound is evaluated for viscosity of the melt (at a cutting speed of 50 s "1) and for the microscopic dispersion of the carbon black The microscopic dispersion of the carbon black is evaluated by examining an extruded strip of the semiconductor compound for surface imperfections with a microscope optical and a reflective light source The imperfection area assigned to undispersed carbon black is related to the total area of the tape examined.In this measurement, dust particles and gel polymer are excluded. ., measurements are presented in Table 2 below.

Examples 5 and 6 and Comparative Example 2 Semiconductor materials are prepared as in Example 4, incorporating the carbon black pellets of Examples 2 and 3 and Comparative Example 1, to produce semiconductor compounds for Examples 5 and 6 and Comparative Example 2, respectively. The same measurements of melt viscosity and microscopic dispersion are made as in Example 4. The results are presented in Table 2 below.

T. * 40 TABLE 2 Example 7 The semiconductor compound of Example 4 is evaluated for the release capacity on a cross-linked polyethylene insulation compound. In the semiconductor compound of Example 4, introduces 1% by weight of dicumyl peroxide, using a Brabender mixer. The temperature during processing is maintained below 150 ° C to minimize the composition of the peroxide. The material is then transferred to a hot hydraulic press, maintained at a temperature of 130 ° C, and 1.2 mm thick plates are produced. Polyethylene plates that have a thickness of 2 mm and contain 1% of dicumyl peroxide are also prepared in a way Similary. The two plates are then laminated together at a pressure of 7.03 Kg / cm2 (100 psi) and exposed to a curing cycle of 180 ° C for fifteen minutes. The bonded laminates are allowed to cool to a temperature below 100 ° C under pressure. The delamination force ba or a peel angle of 180 degrees and a separation speed of 10 cm / minute (3.94 inches / minute) is recorded. The tests are conducted twenty-eight times, and the average release force is given in Table 3 *. following .

Examples 8 and 9 and Comparative Example 3 In a manner similar to Example 7, Examples 8 and 9 and Comparative Example 3 evaluate the release capacity on a crosslinked polyethylene insulation composite, of the semiconductor compounds produced in Examples 5 and 6 and Comparative Example 2, respectively. The average release force for each of the materials is presented in Table 3 below.

Example 10 Pellets of carbon black treated with polyethylene glycol are formed, wherein the polyethylene glycol is used as a granulation aid in the production of pellets of carbon black from carbon black in its soft form. In this example, carbon black has a DBP of 143 cmVlOO g and an iodine surface area of 129 mg / g. The carbon black is combined with an aqueous polyethylene glycol binder solution (molecular weight = 1,000) sufficient to produce a treated carbon black having 2% polyethylene glycol by weight of carbon black. The carbon black and the aqueous binder solution are mixed in a continuous pin granulator which operates with a rotor speed of 1,000 rpm and a mass flow rate of 385.5 Kg / hour (850 lbs / hour). The pellets are collected and dried in a hot air circulation oven maintained at a temperature of 125 ° C until the moisture content is reduced to below about 0.5%. The carbon black pellets produced in this way are evaluated for the resistance of the # pellets and the wear resistance by rubbing 10 as described above. The results of these measurements are presented in Table 4 below.

Examples 11-14 Prepared carbon black pellets treated with polyethylene glycol as in Example 10, except that the molecular weight of the polyethylene glycol contained in the aqueous binder solution is 8,000 (Example 11), 20,000 (Example 12), 35,000 (Example 13) and 20 100,000 (Example 14). In the case of Example 14, the binder solution contains the polyethylene glycol in an amount sufficient to produce a treated carbon black having 1% polyethylene glycol by weight of carbon black. The same measurements of pellet resistance and wear by Rubbing of the pellets, as in Example 10, and the results are presented in Table 4 below.

Comparative Example 4 Carbon black pellets are prepared according to Example 10, except that the binder solution consists only of water, for example, it does not contain polyethylene glycol. The same 10 measurements of resistance and wear by rubbing "the pellets" are performed, as in Example 10, and the results are presented in Table 4.

TABLE 4 Example 15 Semiconductor compounds are produced using the carbon black pellets treated with polyethylene glycol produced in Example 10 above. The carbon black pellets are individually compounded with three different polymers using a Brabender mixer. The compounds # contain 40% carbon black and 60% polymer in 10 weight. The three polymers are 1) an ethylene / vinyl acetate copolymer containing 40% vinyl acetate and having a melt index of 3; 2) an ethylene / vinyl acetate copolymer containing 18% vinyl acetate and having a melt index of 2.5; and 3) an ethylene / ethyl acrylate copolymer containing 18% ethyl acrylate and having a melt index of 3.4. The resulting compounds are evaluated for the melt viscosity (at a cut-off speed of 50 sec. 1 and 130 ° C), as described above The results of these measurements are presented in Table 5 below.

Examples 16-19 and Comparative Example 5 Semiconductor materials are prepared as in Example 15, incorporating the carbon black pellets of Examples 11-14 and Comparative Example 4, to produce semiconductor compounds for Examples 16-19 and Comparative Example 5, respectively. The same measurements of the melt viscosity as in Example 15 are made. results are given in Table 5 below.

TABLE 5 In addition, all of Examples 15-19 show that an addition of polyethylene glycol to treat carbon black results in an improvement in carbon black dispersion.

Examples 20-36 and Comparative Example 6 The carbon black compounds suitable for pigment protection against light ultraviolet are prepared as follows. Carbon black with a DBP of 145 cm3 / 100 g and an iodine surface area of 70 mg / g are granulated with various aqueous solutions of varying concentrations of polyethylene glycol in a spike granulator operating with a rotor speed of 1,050 rpm. In the case of Comparative Example 6, the carbon black is granulated with a 6% aqueous solution, without polyethylene glycol. The pellets are collected and dried in a hot air circulation oven maintained at a temperature of 125 ° C until the moisture content is reduced to below 0.5%. The pellets are evaluated for the pellet strength according to ASTM D 1937 and the friction wear of the pellets according to the modified version of ASTM D The results are presented in Table 6. Several of the carbon black pellets are then compounded with low density polyethylene, having a melt index of 26, to produce a batch. master pigment at 40%. The polyethylene compounds are then evaluated for the viscosity of the /? _ £ _. melted at 130 ° C and at a cutting speed of 50 s "1. The results are shown in Table 6. 10 TABLE 6 TABLE 6 (continued) In all Examples 10 to 36, the incorporation of polyethylene glycol contributes to the improved pellet strength and to the highest wear resistance by rubbing. The results also appear to be independent of the molecular weight of polyethylene glycol. The viscosity of the master batch of carbon black is also decreased by the incorporation of polyethylene glycol as a binder material. Polyethylene glycol also allows for easier incorporation into a film or extruder profile where the final concentration of carbon black is in the range of 0.5% to 4.0%, depending on the final application. In addition, samples of a composition with a charge of 2.5% carbon black in low density polyethylene (LDPE) having a melt index of 0.7, are prepared to simulate a film application. A visual inspection of the samples qualitatively indicates an improvement in the dispersion of the carbon black.

Examples 37-38 and Comparative Example 7 Carbon black compounds are prepared, suitable for use as master batches. The carbon black with a DBP of 135 cm3 / 100 g and an iodine surface area of 180 mg / g, is granulated with various aqueous solutions of varying concentrations of polyethylene glycol in a spigot 20 granulator operating with a rotor speed of 1,100 rpm . The aqueous solutions of Examples 37 and 38 include polyethylene glycol (molecular weight = 35,000) sufficient to provide levels in the carbon black pellets of 2% and 16%, respectively. Comparative Example 25 uses a 100% aqueous solution. The pellets are harvested and dried in a hot air circulation oven maintained at a temperature of 125 ° C until the moisture content is reduced to below about 0.3%. The dry carbon black pellets are then compounded with polyethylene of low density, having a melt index of 26, to produce a master batch that has 40% carbon black by weight. The pellets of carbon black and polyethylene of 10 ba at density are mixed in a Brabender mixer with an initial temperature of 115 ° C and speed of 50 rpm. The polyethylene compounds are then measured for the melt viscosity at 130 ° C and at a cutting speed of 50 sec "1. The results are presented in Table 7.

TABLE 7 Examples 39-40 and Comparative Example The compounds are prepared according to Examples 37-38 and Comparative Example 7, except that the carbon black feedstock has a DBP of 136 cVlOO g and an iodine surface area of 120 mg / g. The same masterbatch compositions are prepared and tested, with the results presented in Table 8. 10 TABLE 8 Example Viscosity Percent Resistance of # Pellets Powder Cast (Pa) Kg (Ibs) 5 min 10 min Comp 8 28.0 (61.9) 0.8 5.2 4.591 39 60.3 (133) 0.1 0.3 3, 804 40 71.2 (157) 0.05 0.12 2, 689 Examples 41-45 The carbon blacks treated with polyethylene glycol are prepared as described in Example 1 above. The treated carbon blacks are prepared by using various amounts of polyethylene glycol as a treatment compound for carbon black. Specifically, the five carbon blacks are prepared using the following types and amounts of polyethylene glycol as a treatment compound.

Black Molecular Weight of Parts by Weight of Coal. # Black Carbon Polyethylene Glycol 3 35, 000 2.0 4 35, 000 3.0 5 100, 000 2.0 Here, it is also noted that polyethylene glycol of 100,000 molecular weight is also known as a polyethylene oxide compound. The semiconductor shields for use in the preparation of electric cables are prepared by combining approximately 57 parts by weight of a copolymer / 1-butene (15% butene content), approximately 41 parts by weight of one of the blacks carbon treated and approximately 1.5 parts by weight of other additives. The ethylene / 1-butene copolymer has a melt index of 27, a density of 0.9 g / cm3 and a molecular weight distribution (MWD) of * í ?? 2.15. The additives include about 0.5% of any antioxidant (such as 1,2-dihydro-2,2,4-trimethylquinoline, 3, 5-diter-butyl-4-hydroxyhydrocinnamate octadecyl or a mixture thereof) and 1.0% of an organic peroxide curative a, a, bis (tert-butylperoxy) -diisopropylbenzene. The specific proportions of the components are as follows: Component 41 42 43 44 45 Ethylene / 1-butene 57.55 56.73 57.55 57.14 57.55 Carbon Black # 1 40.95 Carbon Black # 2 41.77 Carbon Black # 3 40.95 Carbon Black # 4 41.36 Carbon Black # 5 - - - - 40.95 Antioxidant 0.50 0.50 0.50 0.50 0.50 Healing Peroxide 1.00 1.00 1.00 1.00 1.00 Total 100.00 100.00 100.00 100.00 100.00 The components are mixed in a mixer Banbury or other appropriate equipment. The formulations are tested for the different * physical and electrical characteristics. The cure data is determined by measuring the torsion in Kg-cm (pound-inch) on plates of the formulation with an Oscillating Disc Rheometer (ODR) operating at 204 ° C (400 ° F) and 3 ° arc. . The ODR low (Mi) and high (Mh) torsion values, the surface burn time (ts2) and the healing times of 50% (tc (50)) and 90% (tc (90)) ), are presented in Table 10 below. The formulation is also evaluated for volume resistivity at various temperatures, tensile strength and elongation, and extrusion parameters on a Haake Rheocord apparatus. The results are presented in Table 9 below.

Comparative Examples 9-13 Semiconductor shields are prepared for use in the preparation of electric cables, similar to those in Examples 41-45 above, except that carbon black is an untreated carbon black. 20 That is, the carbon black pellets are derived from carbon black granulated with deionized water. The semiconductor shields for use in the preparation of electrical cables are prepared by the combination of approximately 57 parts by weight of an ethylene / 1-butene copolymer (the same copolymer as used in Examples 41-45), approximately 41 parts by weight of the untreated carbon black, and approximately 1.5 parts by weight of other additives. The formulation also includes polyethylene glycol (PEG) added directly to the formulation. In these Comparative Examples, various amounts of polyethylene glycol of different molecular weights are added to the formulations. The specific proportions of the components are as follows: Component Comp 9 Comp 10 Comp 11 Comp 12 Comp 13 Carbon Black 40.13 40.13 40.13 40.13 40.13 Ethylene / 1-butene 57.55 56.73 57.55 56.73 57.55 MW PEG = 20, 000 0.82 MW PEG = 20, 000 1.64 MW PEG = 35 , 000 0.82 PEG of PM = 35, 000 1.64 PEG of MW = 100,000 - - - - 0.82 Antioxidant 0.50 0.50 0.50 0.50 0.50 Healing Peroxide 1.00 1.00 1.00 1.00 Total 100.00 100.00 100.00 100.00 100.00 Here, all parts by weight are based on the weight of the total formulation. The components are mixed in a Banbury mixer or other appropriate equipment as in Examples 41-45 above. It is also noted here that the additives in Comparative Examples 9-13 are the same as those in Examples 41-45, and are present in the same amounts. In addition, the amounts of polymer, carbon black and polyethylene glycol are the same in Examples 41-43 and 45, and Comparative Examples 9-11 and 13, respectively. It should be noted that in Example 44, 10 the amount of polyethylene glycol used is 3% in > , weight of carbon black, and used as a treatment compound on carbon black. Comparative Example 12 contains polyethylene glycol in an amount of 4% by weight of the carbon black and is added directly into the formulation. Also, as £ * < B__ noted above, polyethylene glycol in Examples 41-45 is used to treat carbon black, while in Comparative Examples 9-13, it is added directly to the formulation. The same tests and measurements are conducted as in Examples 41-45, and the results are presented in Table 9. ________fc_____2_a___ __ «_____ £ _ • * < • TABLE 9 U 0 # _tei ss o ^ s > F2 Examples 46-50 Semiconductor shields are prepared for use in the preparation of electrical cables by the combination of approximately 48 parts by weight of an ethylene / vinyl acetate copolymer (50% vinyl acetate content), approximately 11.08 parts by weight of a ethylene / octene copolymer, about 37 parts by weight of one of the blacks carbon treated, prepared for Examples 41-45 above, and about 3.5 parts by weight of other additives. The ethylene / vinyl acetate copolymer has a melt index of between 7 and 11. The ethylene / octene copolymer has a melt index of 31 and a density of 0.87 g / cm3. The additives include approximately 0.9% of a stearic acid processing aid, 0.7% of an antioxidant of 1,2-dihydro-2,2,4-trimethylquinoline, 1.0% of a curative organic peroxide of a, to x-bis ( tert-butylperoxy) -diisopropylbenzene and 0.9% hydrotalcite. The proportions of the specific components are as > follow: Component 46 47 48 49 50 Ethylene / Acetate 48.22 47.40 48.22 47.81 48.22 Black Carbon # 1 37.20 Black Carbon # 2 38.02 Carbon Black # 3 37.20 Carbon Black # 4 37.61 Carbon Black # 5 37.20 Ethylene / Poly ero 11.08 11.08 11.08 11.08 11.08 octene Antioxidant 0.70 0.70 0.70 0.70 0.70 Stearic acid 0.90 0.90 0.90 0.90 0.90 Hydrotalcite 0.90 0.90 0.90 0.90 0.90 Healing peroxide 1.00 1.00 1.00 1.00 Total 100.00 100.00 100.00 100.00 100.00 The components are mixed in a Banbury mixer. The same tests and measurements as in Examples 41-45 are conducted, and the results are presented in Table 10. In addition, the formulations are tested for crosslinked polyethylene adhesion, and the results are also presented in Table 10.

Comparative Examples 14-18 Semiconductor shields for use in the preparation of electric cables are prepared in a manner similar to those in Examples 46-50 above, except that carbon black is an untreated carbon black. That is to say, the carbon black pellets are derived from carbon black granulated with deionized water.10 Semiconductor shields are prepared for use in the preparation of electric cables by the combination of approximately 48 parts by weight of the ethylene / acetate copolymer. of vinyl (50% vinyl acetate content) and approximately 11 parts by weight of the ethylene / octene copolymer both as used in Examples 46-50, about 37 parts by weight of the untreated carbon black, and about 3.5 parts by weight of other additives. The formulation also includes polyethylene glycol (PEG) added directly to the formulation. In these Comparative Examples, varying amounts of polyethylene glycol of different molecular weights are added to the formulations. The proportions of the specific components are as follows: & aa g & pal &< _ • Component Comp Comp 15 Comp 16 Comp 17 Comp 18 Carbon Black 36.38 36.38 36.38 36.38 36.38 Ethylene / acetate 48.22 47.56 48.22 47.56 48.22 vmilo MW PEG = 20,000 0.82 MW PEG = 20, 000 1.64 MW PEG = 35, 000 0.82 MW PEG = 35, 000 1.64 MW PEG = 100,000 0.82 Polymer of 11.08 10.92 11.08 10.92 11 ,, 08 ethylene / octene Antioxidant 0.70 0.70 0.70 0.70 0.70 Stearic Acid 0.90 0.90 0.90 0.90 0.90 Hydrotalcite 0.90 0.90 0.90 0.90 0.90 Healing Peroxide 1.00 1.00 1.00 1.00 1.00 Total 100.00 100.00 100.00 100.00 100.00 Here, all parts by weight are based on the weight of the total formulation. The components are mixed in a Banbury mixer as in Examples 46-50 above. It is also noted here that the additives in Comparative Examples 14-18 are the same as those in Examples 46-50, and are present in the same amounts. In addition, the amounts of polymer, black and polyethylene glycol are the same in E 6-48 and 50, and Comparative Examples 14-16 and 18, respectively. As between Example 49 and Comparative Example 17, the difference is that the amount of polyethylene glycol used in Example 49 is 3% by weight of carbon black (and is used to treat carbon black), but in Example Comparative 17, 4% polyethylene glycol by weight of carbon black is used, as a direct additive to the formulation. In addition, as noted above, the polyethylene glycol in Examples 46-50 is used to treat carbon black, while in Comparative Examples 14-18 it is added directly to the formulation. The same tests and measurements as in Examples 46-50 are conducted, and the results are presented in Table 10. * < • * ® TABLE 10 (continued! ^ * Comparative Examples 19-20 Additional polymer compositions are prepared to compare the results obtained in the above Examples and Comparative Examples with the polymer formulations that do not include the polyethylene glycol compound either as a granulation aid for the treatment of carbon black or as a direct additive. A semiconductor formulation is prepared as in Comparative Examples 9-13 except that the formulation contains approximately 58 parts by weight of an ethylene / 1-butene copolymer (the same copolymer as used in Examples 41-45), about 40.5 parts by weight of the untreated carbon black, and about 1.5 parts by weight of the other additives. The formulation is denoted Comparative Example 19. The additives in Comparative Example 19 are the same as those in Examples 41-45 and Comparative Examples 9-13, and are present in approximately the same amounts, except for the exclusion of the polyethylene glycol compound. A semiconductor formulation is prepared as in Comparative Examples 14-18, except that the formulation contains 48.9 parts by weight of the ethylene / vinyl acetate copolymer (50% vinyl acetate content) and 11.24 parts by weight of the ethylene / octene copolymer used in Examples 46-50, about 36.4 parts by weight of untreated carbon black, and about 3.5 parts by weight of the other additives. The formulation is denoted Comparative Example 20. The additives in Comparative Example 20 are the same as those in Examples 46-50 and Comparative Examples 14-18, and they are present in approximately the same amounts, except for the exclusion of the polyethylene glycol compound. The components for each formulation are mixed in a Banbury mixer or other appropriate equipment as in Examples 41-45 above. The formulations are then tested and measured as in Examples 41-45, and the results are presented in Table 11. For ease of comparison, the results of Comparative Examples 9 and 14 and Examples 41 and 46 are reproduced in Table 11 Table 11 thus shows the results for the two different polymer formulations not containing polyethylene glycol (Comparative Examples 19 and 20), formulations containing polyethylene glycol in an amount of 2% by weight of carbon black as a direct additive to the formulations (Comparative Examples 9 and 14), and formulations containing polyethylene glycol in an amount of 2% by weight of carbon black as a treatment agent for carbon black (Examples 41 and 46). Á & F? TABLE 11 lft______r_ ____ a ___? _ asi Éwte.

TABLE 11 (last) It is intended that the foregoing embodiments illustrate and not limit the present invention. It will be apparent that various modifications can be made. without departing from the spirit and scope of the invention, as defined by the appended claims.

It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property:

Claims (40)

1. A treated carbon black, characterized in that it comprises carbon black treated with at least one polyethylene glycol having a molecular weight of from about 1,000 to about 1,000,000.

2 . A carbon black treated in accordance with claim 1, characterized in that the Polyethylene glycol is present in an amount from about 0.1% to about 50% by weight of the carbon black.

3. A carbon black treated in accordance 15 with claim 1, characterized in that the polyethylene glycol is present in an amount from about 0.1% to about 20% by weight of the carbon black.

4. A carbon black treated in accordance with claim 1, characterized in that the polyethylene glycol is present in an amount of about 1% to about 10% by weight of the carbon black.

5. A carbon black treated in accordance with claim 1, characterized in that the polyethylene glycol has a molecular weight greater than 20,000 to about 100,000.

6. A carbon black treated in accordance with claim 1, characterized in that the polyethylene glycol has a molecular weight from about 35,000 to about 100,000.

7. A carbon black treated in accordance with claim 1, characterized in that the treated carbon black is in a granular form.

8. A process for the preparation of a treated carbon black, characterized in that it comprises the treatment of a carbon black with at least one polyethylene glycol having a molecular weight of from about 1,000 to about 1,000,000, 20 to produce the treated carbon black.

9. A process according to claim 8, characterized in that the polyethylene glycol is present in an amount of about 0.1% up to about 50% by weight of the treated carbon black.

10. A polymeric formulation, characterized 5 because it comprises at least one polymer and a carbon black treated with at least one polyethylene glycol having a molecular weight of from about 1,000 to about 1,000,000.

11. A polymeric formulation according to claim 10, characterized in that the polymer is selected from the group consisting of homopolymers, copolymers and grafted polymers of ethylene, natural rubber elastomers, polybutadiene, Polyisoprene, random styrene-butadiene rubber, polychloroprene, nitrile rubbers, ethylene / propylene copolymers and terpolymers, styrene homopolymers and copolymers, linear and branched polyether or polyester polyols, polyesters and 20 crystalline and amorphous polyamides, alkyd resins, turpentine resin acids, turpentine resin esters, hydrocarbon resins produced from thermal polymerization or Friedal Crafts of cyclic diene monomers, ethylene / silane copolymers, ethylene terpolymers -olefin / diene, and hydrocarbon oils, and mixtures thereof.

12. A polymeric formulation according to claim 10, characterized in that the polymer is a polymer, copolymer or terpolymer containing at least one polyolefin.

13. A polymeric formulation according to claim 10, characterized in that the polyethylene glycol has a molecular weight greater than 20,000 to about 100,000.

14. A polymeric formulation according to claim 10, characterized in that the polyethylene glycol has a molecular weight of about 35,000 to about 100,000.

15. A polymeric formulation according to claim 10, characterized in that the polyethylene glycol is present in an amount from about 0.1% to about 50% by weight of the treated carbon black.

16. A polymeric formulation according to claim 10, characterized in that the treated carbon black is present in an amount from about 0.1% to about 65% by weight of the formulation.

17. A polymeric formulation according to claim 10, further characterized in that it comprises at least one additive selected from the group 10 consists of crosslinking agents, vulcanizing agents, stabilizers, antioxidants-, processing aids, pigments, dyes, metal deactivators, oil extenders, lubricants, and inorganic fillers.

18. A polymeric formulation according to claim 12, characterized in that the polymer is a copolymer of ethylene with at least one monomer selected from the group consisting of acetate 20 of vinyl, alkyl acrylates of 1 to 8 carbon atoms, alkyl methacrylates of 1 to 8 carbon atoms, and alpha-olefins.

19. A polymer formulation of compliance 25 with claim 18, characterized in that the 8β-ethylene copolymer is an ethylene / vinyl acetate copolymer containing vinyl acetate in an amount of about 5 to about 80 mole percent.

20. A polymeric formulation according to claim 18, characterized in that the copolymer of ethylene is ethylene copolymerized with one of methyl acrylate, ethyl acrylate and sodium acrylate. 10 butyl.

21. A polymeric formulation according to claim 20, characterized in that the ethylene copolymer contains alkyl acrylate in 15 an amount from about 5 to about 80 mole percent.

22. A polymeric formulation according to claim 18, characterized in that the Ethylene copolymer is ethylene copolymerized with an alpha-olefin selected from the group consisting of propene, butene, hexene, and octene, the ethylene copolymer contains ethylene in an amount of about 25 to about 98 percent 25 mol.

23. A polymer formulation according to claim 18, characterized in that the formulation comprises from about 30 to about 80 parts by weight of the ethylene copolymer, and from about 12 to about 50 parts by weight of the treated carbon black, based on the total weight of the formulation.

24. A polymeric formulation in accordance with claim 23, characterized in that the treated carbon black is a carbon black treated with polyethylene glycol in an amount from about 1% to about 10% by weight of the treated carbon black.

25. A polymeric formulation according to claim 23, characterized in that it comprises at least one additive selected from the group consisting of crosslinking agents, curing agents, stabilizers, antioxidants, processing aids, pigments, dyes, deactivators, metals, oil extenders, lubricants, and inorganic fillers. * a_ ^ ¡_?

26. A polymeric formulation according to claim 23, further characterized in that it comprises an ethylene / octene copolymer in an amount from about 2% to about 30% by weight of the formulation.

27. A "polymeric" formulation according to claim 18, characterized in that the formulation comprises from about 40 to about 90 parts by weight of an ethylene / α-olefin copolymer and from about 10 to about 50 parts by weight of the black of treated coal, based on the total weight of the formulation.

28. A polymeric formulation according to claim 27, characterized in that the ethylene / α-olefin copolymer is an ethylene / butene copolymer.

29. A polymeric formulation according to claim 27, characterized in that the ethylene / α-olefin copolymer is an ethylene / propylene copolymer.

30. A polymeric formulation according to claim 27, characterized in that the treated carbon black is a carbon black treated with polyethylene glycol in an amount from about 1% to about 10% by weight of the treated carbon black.

31. A polymeric formulation according to claim 27, further characterized in that it comprises at least one additive selected from the group consisting of crosslinking agents, vulcanizing agents, stabilizers, antioxidants, processing aids, pigments, dyes, metal deactivators. , oil extenders, lubricants, and inorganic fillers.

32. An electrically conductive device, characterized in that it comprises an insulating material, an electrical conductor and the polymer formulation according to claim 10.

33. An electrically conductive device according to claim 32, characterized in that the polymer formulation is attached to the electrical conductor. __ £ _________________________________________ «zt

34. An electrically conductive device according to claim 32, characterized in that the polymer formulation is attached to the insulating material.

35. An electrically conductive device according to claim 32, characterized in that the polymer formulation is coated on * the insulating material, and wherein the polymeric formulation can be removed detachably from the insulating material.

36. An electrically conductive device according to claim 32, characterized in that the electrical conductor comprises a plurality of conductive wires and the polymeric formulation forms a filler material between the conductive wires.

37. An electrically conductive device according to claim 32, characterized in that the polymer formulation forms a liner around the device. zt

38. An electrically conductive device according to claim 32, characterized in that the device is an electric cable.

39. A shield for an energy cable comprising the polymer formulation according to claim 10, characterized the shielding because the formulation comprises the treated carbon black in an amount sufficient to impart properties 10 semiconductors to the formulation.

40. A shield for an energy cable comprising the polymeric formulation according to claim 10, characterized in that the The formulation comprises the carbon black treated in a sufficiently low amount so as not to impart conductive properties to the insulating material. & * J - ^^^ íB »I