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    • 专利摘要:
    semiconductor polyolefin composition comprising conductive charge. the present invention relates to a semiconductor polyolefin composition comprising graphene nanoplatelets. also refers to a semiconductor paliolefin composition comprising the combination of graphene and carbon black nanoplatelets. moreover, the present invention relates to a process for producing the semiconductor polyolefin composition as well as the use of the semiconductor polyofefin composition in a power cable. moreover, the invention also relates to an article, preferably a power cable comprising at least one semiconductor layer comprising said polyolefin composition.
    公开号:BR112012025245B1
    申请号:R112012025245
    申请日:2011-04-05
    公开日:2019-12-17
    发明作者:Svanberg Christer；Costa Francis；Ali Malik Muhammad；Uematsu Takashi；Gkourmpis Thomas；Pham Tung；Liu Yi
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for POWER CABLE AND USE OF A SEMI-CONDUCTIVE POLYOLEFINE COMPOSITION.
    [0001] The present invention relates to a semiconductor polyolefin composition comprising graphene nanoplatelets. It also refers to a semiconductor polyolefin composition comprising the combination of graphene and carbon black nanoplatelets. In addition, the present invention relates to a process for producing the semiconductor polyolefin composition as well as for the use of the semiconductor polyolefin composition in a power cable. In addition, the invention is also related to an article, preferably a power cable comprising at least one semiconductor layer comprising said polyolefin composition.
    [0002] A semiconductor material is defined as a material having an electrical conductivity intermediate between insulators and conductors. A typical electrical conductivity range for semiconductors is in the range of 10 -9 to 10 3 S / cm corresponding to electrical resistivity between 109 to 10 -3 ohm · cm (see, for example, McGrawHill Dictionary of Scientific and Technical Terms, 4 a Edition, p. 1698, 1989).
    [0003] A common means of obtaining a semiconductor polymer composite is to incorporate carbon black into the polymer typically 30 to 50% by weight as, for example, described in United States Patent No. 5,556,697. However, high carbon black charges result in high viscosity of the compounds. Lower carbon black loads are desirable to improve the processability of compounds in cable extrusions while still maintaining high conductivity. One option is carbon black of high structure such as Negro Ketjen. This can reduce the amount required
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    2/35 conductive load, however, due to the high structure the viscosity is drastically increased even at these low loads.
    [0004] Another disadvantage of carbon black charges is that the heating of the volume resistivity (VR) is dramatically increased when the polymer composition is heated to a standard operating temperature of about 90 ° C. Additional carbon black can be included to attenuate the temperature dependence of VR, however, this will result in the worsening of processing properties.
    [0005] Carbon black can be replaced with expanded graphite to increase conductivity, as described in WO 2008/079585. WO 2008/079585 describes a semiconductor composition comprising a polyolefin polymer and an expanded graphite that is contained in the composition in an amount of 0.1 to 35% by weight of the total formulation. The processes for preparing the expanded graphite are also described. However, the charge required for expanded graphite to obtain a substantial increase in conductivity is 10 to 15% by weight, making a significant contribution to viscosity. Even more importantly, large particles of expanded graphite produce a very rough surface, which is undesirable in cable applications. Therefore, there is a need for semiconductor polymeric compositions that combine high conductivity, low viscosity and high surface smoothness.
    [0006] Other options for increasing conductivity in semiconductor materials are the incorporation of carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs). United States Patent Application US 2005/0064177 A1 describes semiconductor compositions with a combination of carbon black (CB) and carbon nanotubes (CNTs). However, the combined CNT and CB loads required to obtain a low resistivity are typically in excess of 15% by weight, which results in a reduced
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    3/35 flow. It is, therefore, desirable to have a semiconductor composition with reduced total charge concentration, allowing smooth surface and good fluidity. In addition, CNTs are currently disadvantaged due to their extremely high price.
    [0007] On the other hand, GNPs have recently discovered applications in electroconductive materials.
    [0008] Possible procedures for producing graphene nanoplatelets and single graphene sheets have been described in, for example, US 2002/054995 A1, US 2004/127621 A1, US 2006/241237 A1 and US 2006/231792 A1. Such processes are, for example, also described by Stankovich et al., Nature 442, (2006) pp.282, and by Schniepp, Journal of Physical Chemistry B.1 10 (2006) p. 853. Non-limiting examples of materials are Vor-X ® supplied by Vorbecks Materials and xGNP ® supplied by XG Science.
    [0009] US2002 / 054995 A1 describes how nanoplatelets can be created by a high pressure mill determining an aspect ratio between the lateral size and thicknesses of 1500: 1 and a thickness of 1 -100 nm.
    [00010] United States Patent No. 7,071,258 describes a process for the production of nanoscale graphene plate material comprising a) partially or completely carbonizing a precursor polymer or heat treating petroleum or tar pitch to produce graphite crystallites. micro and / or nanoscales containing polymeric carbon with each crystallite comprising a sheet or a multiplicity of graphite plane sheets; b) exfoliate the graphite crystallites; and c) mechanical friction treatment. One dimension is less than 100 nm.
    [00011] WO2008 / 045778 A1 describes a process for the functionalization of graphene sheets. The method is based on the addition of solvent to obtain graphite oxide with graphene interlayer.
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    4/35 pacially expanded and subsequently overheating graphite oxide to decompose graphite oxide. The obtained surface area is in the range of 300 to 2600 m 2 / g.
    [00012] However, from the literature reference it can be inferred that an average platelet thickness less than 50 nm cannot be obtained by sonicating expanded graphite materials, see, for example, Chen et al., Polymer 44 (2003 ) P. 1781 and references cited here.
    [00013] Electrically conductive polymer nanocomposites have been described using single-layer or multilayer graphene nanoplugs as in WO2008 / 045778A1 and WO2008 / 143692A1. However, composites with a combination of surface smoothness, low viscosity and low electrical resistivity, have not been described and cable applications are not targeted. This unique combination of properties is central to cable applications, especially semiconductor shields in power cables.
    [00014] In another aspect, mixtures of GNPs and carbon black as a conductive filler are described, for example, United States Patent No. 4,971,726 describes semiconductor composites with carbon black and expanded graphite having an average particle size 40 Dm or more, however, does not consider graphene nanoplatches with a small thickness ratio and large aspects between thickness and diameter. The particularly large size of the expanded graphite leads to the rough surface, and is therefore not suitable for power cable applications. In addition, to obtain suitable electrical properties substantial amounts of expanded graphite and carbon black are required which cause an undesired increase in the viscosity of the compound.
    [00015] The present invention is based on the discovery that a semiconductor polyolefin composition comprising a resin
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    5/35 base olefin polymer and graphene nanoplatelets can achieve the above goals. Especially such a polyolefin composition provides a unique property profile with a combination of low viscosity, smooth surface, low resistivity and low temperature dependence on volume resistivity, which is advantageous for cable applications.
    [00016] In a preferred embodiment of the present invention, the above objectives are achieved by mixing a solid conductive charge other than graphene nanoplatelets with the polyolefin composition described above.
    [00017] The present invention is also directed to an article comprising an inventive semiconductor polyolefin composition. Preferably, the article is a power cable, more preferably a power cable comprising a semiconductor layer comprising the semiconductor polyolefin composition according to the present invention.
    [00018] Still further, the present invention is also concerned with the use of the semiconductor polyolefin composition of the invention in a semiconductor layer of a power cable.
    [00019] In the following, the figures illustrating the present invention are briefly described. In the figures:
    [00020] figure 1 shows optical microscopy photos of the MFR filaments used to determine the surface smoothness of Example No.1;
    [00021] figure 2 shows optical microscopy photos of the MFR filaments used to determine the surface smoothness of Example No.2;
    [00022] figure 3 shows optical microscopy photos of the MFR filaments used to determine the surface smoothness of Comparative Example No.1; and
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    6/35 [00023] figure 4 shows optical microscopy photos of the MFR filaments used to determine the surface smoothness of Comparative Example No.2.
    [00024] Figure 5 shows a heating scan to determine the temperature dependence of the volume resistivity of Example 3, Comparative Example 4 and Comparative Example 5.
    [00025] figure 6 shows a cooling scan to determine the temperature dependence of the volume resistivity of Example 3, Comparative Example 4 and Comparative Example 5.
    [00026] figure 7 shows the annealing dependence of the volume resistivity of Example 3 and Comparative Example 4.
    Detailed Description of the Invention [00027] The present invention describes a semiconductor polyolefin composition with low fill fill concentration that has surprisingly low viscosity, high conductivity, excellent surface smoothness and low temperature dependence on volume resistivity. The invention is based on a semiconductor polyolefin composition in which graphene nanoplatforms (GNP) are used in combination with an olefin-based polymer resin. In a preferred embodiment optionally a solid conductive charge, other than GNP can be used in the semiconductor polyolefin composition of the present invention.
    [00028] Throughout the description of the present invention the term expanded graphite encompasses graphite having no significant order as determined by X-ray diffraction pattern. The expanded graphites have been treated to increase the distance between planar between the individual layers that form the structure of graphite. It is understood that the term expanded graphite throughout this description refers to a graphite material where the distances between the graphene layers have been substantially increased compared to the graphite
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    7/35 te pure. It should be noted in the context of the present invention that the general expanded graphite structures do not necessarily form graphene nanoplatelets (GNP's) as defined by this invention. [00029] Graphene nanoplatelets (GNPs) are characterized by the fact that the material is composed of one or more layers of two-dimensional hexagonal lattice. The platelets have a length parallel to the graphite plane, below the labeled diameter, and a thickness orthogonal to the graphite plane, below the labeled thickness. Another characteristic feature of GNPs is that platelets are very thin even though they have a large diameter, so GNPs have a very large aspect ratio. The typical thickness of graphene nano-platelets is 100 nm or less, preferably 40 nm or less, more preferably 20 nm or less or 10 nm or less. The included lower limit of graphene nanoplatforms are unique graphene sheets. The thickness of a single sheet of graphene is about 1 nm, as, for example, measured with atomic force microscopy (AFM) described in detail, for example, by Stankovich et al., Nature 442, (2006), pp. 282. The side diameter on the other hand, which can also be measured with AFM, is typically 200 micrometers or less, preferably 50 micrometers or less or even more preferably 10 micrometers or less. The lateral extension can be controlled by, for example, grinding to the desired size.
    [00030] It is preferable that the aspect ratio between diameter and thickness is 50 or more, more preferably above 500 and more preferably above 1000.
    [00031] The BET value of graphene nanoplatelets is typically above 80 m 2 / g, and can even be up to 2500 m 2 / g for materials with a large fraction of single graphene sheets (ASTM D3037).
    [00032] In another aspect graphene nanoplets also include graphene platelets that are a little rough, such as
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    8/35 example, described in Stankovich et al., Nature 442, (2006), pp. 282. Additionally, graphene materials with roughness for another essentially flat geometry are included. Also more complex secondary structures such as cones are also included, see, for example, Schniepp, Journal of Physical Chemistry B.1 10 (2006) pp. 8535. The definition of GNP does not include carbon nanotubes.
    [00033] In another aspect, GNPs can be functionalized to improve interaction with base resins. Non-limiting examples of surface modifications include treatment with nitric acid treatment; Plasma O2; UV / Ozone; the mine; acrylamine as described in US2004 / 127621 A1.
    [00034] A specifically preferred embodiment of the graphene nanoplatelets used in the present invention is the commercial product xGNP from XG Science.
    [00035] In one aspect, the present invention relates to a semiconductor polyolefin composition comprising an olefin-based polymer resin, optionally being a polymeric mixture comprising one or more olefin polymers, and graphene nanoplatforms, the nanoplatelets being of graphene are contained in the total composition with a percentage by weight including, but not limited to, 2% by weight to 20% by weight, preferably 2 to 15% by weight. In addition, preferred weight ranges can be 4 to 15% by weight, more preferably 4 to 14% by weight, and more preferably 6 to 12% by weight. The lower limit is due to electrical requirements and the upper limit is due to the limitation in viscosity and surface roughness of the composition.
    [00036] In another aspect, graphene nanoplatelets have an average platelet thickness of 50 nm or less, preferably 40 nm or less, preferably 20 nm or less.
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    [00037] In yet another aspect the present invention relates to graphene nanoplatelets having an aspect ratio of the length divided by the thickness of 50 or more that can be measured by atomic force microscopy (AFM).
    [00038] The semiconductor polyolefin composition as defined in claim 1 surprisingly provides a combination of advantages. It improves not only processability due to comparatively lower viscosity (higher MFR2 values) than conventional semiconductor polyolefin compositions containing carbon black as the conductive filler. Unexpectedly, the GNP present as a conductive charge provides in smaller charges the same or even improved level of conductivity compared to conventional carbon blacks. In this way, a suitably low volume resistivity is obtained. In addition, the incorporation of GNP in semiconductor polyolefin compositions produces excellent surface smoothness when expressed by surface roughness calculated as the R_RMS. The method is detailed below. These excellent surface smoothness cannot be achieved by using general purpose expanded graphite, which generally has very high particle dimensions, determining increased surface roughness.
    [00039] Preferably, the semiconductor polyolefin composition according to the present invention has surface roughness characterized by R_RMS, measured in extruded samples, of 100 micrometers or less.
    [00040] It was also surprisingly found that the semiconductor polyolefin composition according to the present invention has a higher temperature dependence on volume resistivity compared to the respective semiconductor polyolefin compositions based on carbon black. It was also found that the
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    10/35 electrical performance such as VR of the semiconductor polyolefin composition according to the present invention provides under annealing at temperatures below the melting temperature of the polymer, which is not observed in semiconductor polyolefin compositions based on carbon black.
    [00041] According to a preferred embodiment of the invention, the semiconductor polyolefin composition comprises an olefin-based polymer resin which can be a polymeric mixture comprising one or more olefin polymers, and a combination of graphene nanoplatforms and a filler solid conductor. In an even more preferred embodiment, the solid conductive charge is carbon black.
    [00042] Preferably, said carbon black fulfills at least one of the following requirements:
    an iodine number of at least 30 mg / g, measured according to ASTM D 1510, a DBP oil absorption number of at least 30 ml / 100 g, measured according to ASTM D 2414, a nitrogen surface area BET of at least 30 m 2 / g, measured according to ASTM D 3037, a statistical surface area (STSA) of at least 30 m 2 / g measured according to ASTM D5816.
    [00043] Preferably, said carbon black fulfills any combination of said requirements, more preferably all of said requirements.
    [00044] The solid conductive charge may be contained in the composition with a fraction of 5 to 95% by weight, preferably 10 to 80% by weight, more preferably 20 to 60% by weight and even more preferably 25 to 50% by weight, in relation to the weight of graphene nanoplatches.
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    11/35 [00045] It is intended throughout the present description that the term solid conductive charge covers any type of charge that is electrically conductive and can be dispersed in a polymer. Non-limiting examples are electrically conductive carbon black and intrinsically conductive polymers. Any carbon black that is electrically conductive can be used. Preferably carbon black has one or more of the following properties: i) iodine number of at least 30 mg / g according to ASTM D1510, ii) oil absorption number of at least 30 ml / 100g which is measured according to with ASTM D2414, iii) nitrogen surface area (BET measurement) of at least 30 m 2 / g according to ASTM D3037, and iv) statistical surface area (STSA) of at least 30 m 2 / g according to ASTM D5816. Non-limiting examples of preferable carbon blacks include oven carbon black and acetylene blacks. Non-limiting examples of intrinsic conductive polymers include poly (pphenylenovinylene), polyfluorene, polyaniline and polythiophene.
    [00046] It was unexpectedly discovered that with the combination of GNPs and carbon black in the olefin-based polymer resin all the advantages described above are retained with the also unexpected reduction in resistivity and viscosity, at the same time as the additional improvement surface smoothness and less dependence on resistivity temperature is obtained. Additionally, a self-healing effect was observed, that is, during the operation of the cable, the electrical performance will improve over time under annealing.
    [00047] Throughout this invention the term polyolefin or olefin polymer encompasses both an olefin homopolymer and a copolymer of an olefin with one or more comonomer (s). Also known as a comonomer refers to copolymerizable comonomer units.
    [00048] The polyolefin can be any polyolefin suitable for
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    12/35 a semiconductor layer. Preferably, the polyolefin is an olefin copolymer or homopolymer that contains one or more comonomer (s), more preferably an ethylene homo- or copolymer or a propylene homo- or copolymer, and more preferably a polyethylene, which can be made from a low pressure process or a high pressure process. The polyolefin can be, for example, a commercially available polymer or it can be prepared according to or analogously to the known polymerization process described in the chemical literature.
    [00049] When polyolefin, preferably polyethylene, is produced in a low pressure process, then it is typically produced by a coordination catalyst, preferably selected from a Ziegler Natta catalyst, a single site catalyst, which comprises a metallocene catalyst and / or non-metallocene, and / or a Cr catalyst, or any mixture thereof. The polyethylene produced in a low pressure process can have any density, for example, be a very low density linear polyethylene (VLDPE), a low density linear polyethylene (LLDPE) copolymer with one or more comonomers, polyethylene of medium density (MDPE) or high density polyethylene (HDPE). The polyolefin can be unimodal or multimodal with respect to one or more of the molecular weight distribution, comonomer distribution or density distribution. As a modality, low pressure polyethylene can be multimodal with respect to molecular weight distribution. Such multimodal polyolefin can have at least two polymer components that have a different average molecular weight, preferably a lower average molecular weight (LMW) and a higher average molecular weight (HMW). A unimodal polyolefin, preferably low pressure polyethylene, is typically prepared using a single stage polymerization,
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    13/35 for example, gas phase solution, suspension or polymerization in a manner well known in the art. A multimodal polyolefin (for example, bimodal), for example, a low pressure polyethylene, can be produced mechanically by mixing two or more, separately prepared polymer components or by mixing in situ in a multistage polymerization process during the preparation process polymer components. Both mechanical and in situ mixing is well known in the field. A multistage polymerization process can preferably be carried out on a series of reactors, such as a loop reactor which can be a suspension reactor and / or one or more gas phase reactors. Preferably a loop reactor and at least one gas phase reactor are used. Polymerization can also be preceded by a prepolymerization step.
    [00050] When the polyolefin, preferably polyethylene, is produced in a high pressure process, an LDPE homopolymer or an ethylene LDPE copolymer with one or more comonomers can be produced. In some embodiments, the LDPE copolymer or homopolymer may be unsaturated. For the production of ethylene (co) polymers by high pressure radical polymerization, reference can be made to the Encyclopedia of Polímero Science and Engineering, Vol. 6 (1986), pp 383-410 and Encyclopedia of Materials: Science and Technology, 2001 Elsevier Science Ltd .: Polyethylene: High-pressure, R.KIimesch, D.Littmann and F.-O. Mahling pp. 7181 7184.
    [00051] In another aspect, polyolefin polymers include, but are not limited to, ethylene and unsaturated ester copolymers with an ester content of at least about 50% by weight, based on the weight of the copolymer. Non-limiting examples of unsaturated esters are vinyl esters, acrylic acid and acid esters
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    14/35 methacrylic, typically produced by conventional high pressure processes. The ester can have 4 to about 20 carbon atoms, preferably 4 to 10 atoms. Non-limiting examples of examples of vinyl esters are: vinyl acetate, vinyl butyrate, and vinyl pivalate. Non-limiting examples of acrylic and methacrylic acid esters are: methyl acrylate, ethyl acrylate, tbutyl acrylate, n-butyl acrylate, isopropyl acrylate, hexyl acrylate, decyl acrylate and lauryl acrylate. An exemplary polyolefin that can be used in the present invention is Escorene 783 commercially available from ExxonMobile.
    [00052] In another aspect of this invention the polyolefin is ethylene / a-olefin elastomeric copolymers having an α-olefin content of 15% by weight, preferably 25% by weight or more, based on the weight of the copolymer. Such copolymers typically have an α-olefin content of 50% by weight or less, preferably 40% by weight or less and more preferably 35% by weight or less, based on the weight of the copolymer. Α-olefin content is measured by 3 C nuclear magnetic resonance (NMR) spectroscopy as described by Randall (Re. Macromolecular Chem. Phys. C29 (2 & 3)). Α-olefin is preferably a linear, branched or cyclic C3-20 α-olefin. The term copolymer refers to a polymer made up of at least two monomers. This includes, for example, copolymers, terpolymers and tetrapolymers. Examples of C3-20 α-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1hexadecene and 1-octadecene. Α-olefins can also contain a cyclopentane or cyclohexane of cyclic structure, resulting in an αolefin such as 3-cyclohexyl-1-propene and vinyl cyclohexane. Although not α-olefins in the classic sense of the term, for the purpose of this invention certain cyclic olefins such as norbornene and related olefins, in particular 5-ethylidene-2-norborene, are covered by
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    15/35 term α-olefins and can be used as described above. Similarly, styrene and its related olefins, for example αmethylstyrene, etc. are α-olefins for the purpose of this invention, Illustrative examples of copolymers include ethylene / propylene, ethylene / butane, ethylene / 1-hexene, ethylene / 1-octene, ethylene / styrene and the like. Illustrative examples of terpolymers include ethylene / propylene / 1-octene, ethylene / butane / 1-octene, ethylene / propylene / diene monomer (EPDM) and ethylene / butane / styrene. The copolymer can be random or in blocks.
    [00053] In another aspect of this invention the polyolefin can comprise an olefin polymer with hydrolyzable silane groups and optionally a silanol condensation catalyst. The polymer composition according to this aspect is preferably an ethylene homopolymer or ethylene copolymer containing crosslinkable silane groups, which have been introduced by copolymerization or grafting polymerization. Non-limiting examples of preferred silane compounds are vinyltrimethoxy silane, vinylbismethoxyethoxy silane, vinyltriethoxy silane, gamma- (meth) acryloxypropyltrimethoxy silane, gamma- (meth) -acryloxy-propyltriethoxy silane and vinyltriacetoxy silane. Preferably, the olefin copolymer containing silane or graft polymer is cross-linked under the action of water and a silanol condensation catalyst.
    [00054] Copolymerization can be carried out in the presence of one or more other comonomers that are copolymerizable with the two monomers and which, for example, can comprise one or more selected vinylcarboxylate esters such as vinyl acetate and vinyl pivalate; (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate; (meth) acrylic acid derivatives such as (meth) acrylonitrile and (meth) acrylamide; vinyl ethers, such as vinyl methyl ether and vinyl phenyl ether; alpha olefins such as propi
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    16/35 leno, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene; olefinically unsaturated carboxyl acids, such as (meth) acrylic acid, maleic acid and fumaric acid; and aromatic vinyl compounds, such as styrene and alpha-methyl styrene.
    [00055] Preferred comonomers are mono-carboxylic acid vinyl ethers having 1-4 carbon atoms, such as vinyl acetate and alcohol (meth) acrylate having 1-8 carbon atoms, such as methyl (meth) acrylate. The term (meth) acrylic acid used herein is intended to include both acrylic acid and methacrylic acid. The comonomer content in the polymer can reach 40% by weight or less, preferably 0.5-35% by weight, more preferably 1-25% by weight.
    [00056] According to the invention, the silane-containing polymer contains 0.001-15% by weight of the silane compound, preferably 0.015% by weight and especially preferred 0.1-3% by weight. To facilitate the incorporation of the solid conductive charge in the present invention, it is preferred that the polymer comprises, in addition to ethylene and the silane compound, at least one additional monomer chosen from vinylcarboxylate esters, (meth) acrylates, (meth) acrylic acid derivatives and vinyl ethers mentioned above. This facilitates the mixing of the conductive charge. It is especially preferred that the olefin polymer comprises an ethylene terpolymer, silane monomer and a third comonomer, which can be selected from one or more of C3-C8 alphaolefins; vinyl esters of monocarboxylic acids having 1-4 carbon atoms, preferably vinyl acetate; and (meth) alcohol acrylates having 1-8 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Copolymers of ethylene, silane monomer and methyl-, ethyl- or butyl acrylate are especially preferred.
    [00057] Copolymerization of ethylene, the silane compound does not
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    17/35 and optionally additional comonomers can be performed under any suitable condition resulting in the formation of the desired polymer. The cross-linking of the silane polymer is carried out with the help of a catalyst, preferably a catalyst by condensation of silanol. In general any silanol condensation catalyst can be used in the present invention and a silanol condensation catalyst can be selected from the group consisting of metals carboxylate, such as tin, zinc, iron, lead and cobalt; organic bases, as well as inorganic acids and organic acids. Special examples of silanol condensation catalysts are dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, stannous acetate, stannous caprylate, lead naphthenate, zinc caprylate, cobalt naphthenate, ethyl amines, dibutyl amine, pyridine, hexyl amine, hexyl amine, pyridine, hexyl amine, pyridine, hexyl amine, pyridine, hexyl amine, pyridine, amine, hexyl amine, pyridine, amine. Inorganic acids, such as sulfuric acid and hydrochloric acid, and organic acids, such as toluenesulfonic acid, acetic acid, stearic acid and maleic acid, tin carboxylate are especially preferred catalyst compounds.
    [00058] The amount of silanol condensation catalyst employed is generally in the range of 0.001 to 2% by weight, preferably 0.01 -0.5% by weight, of the amount of polymer containing silane in the composition.
    [00059] Other examples of olefin polymers are: copolymer of polypropylene, propylene; copolymers of polybutene, butene; highly short chain branched α-olefin copolymers with an ethylene comonomer content of 50 mole percent or less; polyisoprene; EPR (ethylene copolymerized with propylene); EPDM (ethylene copolymerized with propylene and a diene such as hexadiene, dicyclopentadiene, or ethylidene norbornene); copolymers of ethylene and an α-olefin having 3 to 20 carbon atoms such as ethylene / octene copolymers; terpolymers of ethylene, α-olefin and a diene; terpolí
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    18/35 mere ethylene, α-olefin, and an unsaturated ester; copolymers of ethylene and vinyl-tri-alkyloxy silane; ethylene terpolymers, vinyl tri-alkoxy silane and an unsaturated ester; or copolymers of ethylene and one or more esters of acrylonitrile and maleic acid. In another embodiment of the present invention, the olefin polymer can comprise ethylene ethyl acrylate. Comonomers can be incorporated randomly or in blocks and / or graft structures.
    [00060] In another embodiment of the present invention the olefin polymer may comprise or may be a heterophasic olefin copolymer, for example, a heterophasic propylene copolymer. The heterophasic propylene copolymer can preferably be a heterophasic copolymer comprising a random propylene copolymer as a matrix phase (RAHECO) or a heterophasic copolymer having a propylene homopolymer as a matrix phase (HECO). A random copolymer is a copolymer where the part of the comonomer is randomly distributed in the polymer chains and also consists of alternating sequences of two monomer units of random length (including single molecules). It is preferred that the random propylene copolymer comprises at least one comonomer selected from the group consisting of ethylene and C4-C8 alpha-olefins. Preferred C4-C8 alpha-olefins are 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene or 1-octene, more preferred 1-butene. A particularly preferred random propylene copolymer can comprise or consist of propylene and ethylene. In addition, the comonomer content of the polypropylene matrix is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight and even more preferably 2 to 7% by weight. To combine optimal processability with the required mechanical properties, the comonomer incorporation can be controlled in such a way that one component of the polypropylene contains more comonomer than the other.
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    19/35
    Suitable polypropylenes are described, for example, in WO 03/002652.
    [00061] According to another embodiment of the present invention the ratio between the MFR2 of the semiconductor polyolefin composition to the MFR2 of the olefin polymer base resin is preferably as high as possible. The increase in the melt flow rate caused by adding the solid conductive charge or the GNP is as low as possible. A high ratio of MFR2 from the semiconductor polyolefin composition to the MFR2 from the olefin polymer base resin is beneficial for processing properties, e.g., burn performance, and mechanical properties. The typical MFR2 of olefin polymers is in the range of 0.1 to 100 g / 10 minutes when measured at 190 ° C for polyethylene, at 230 ° C for polypropylene and a load of 2.16 kg according to ISO 1 133.
    [00062] Preferably, the semiconductor polyolefin composition according to the present invention has an MFR2 ratio of the polyolefin composition to the MFR2 of the olefin polymer base resin of 0.30 or more, the MFR2 being measured in a load of 2.16 kg according to ISO 1 133, at a temperature of 190 ° C for polyethylene and at a temperature of 230 ° C for polypropylene.
    [00063] In one embodiment, the semiconductor polyolefin compositions are crosslinkable. Crosslinkable means that the cable layer can be crosslinked before use in its final application. In the crosslinking reaction of a polymer, interpolymer crosslinks (bridges) are mainly formed. Crosslinking can be initiated by free radical reaction using irradiation or preferably using a crosslinking agent, which is typically a free radical generating agent, or by incorporating crosslinkable groups into polymer components, as known in the art. In addition, in the application of cables, the crosslinking step of the composition sePetição 870190105690, of 10/18/2019, p. 25/51
    20/35 miconductor is typically performed after cable formation.
    The free radical crosslinking agent can be a radical forming crosslinking agent that contains at least one -O-O- bond or at least one -N = N- bond. More preferably, the crosslinking agent is a peroxide, whereby crosslinking is preferably initiated using a well-known peroxide crosslinking technology which is based on free radical crosslinking and is well described in the field. The peroxide can be any suitable peroxide, for example, such conventionally used in the field.
    [00065] As mentioned above, crosslinking can also be achieved by incorporating crosslinkable groups, preferably hydrolyzable silane groups, into the polymer component (s) of the semiconductor composition. Hydrolyzable silane groups can be introduced into the polymer by copolymerizing, for example, ethylene monomers with comonomers containing silane group or by grafting with compounds containing silane groups, that is, by chemical modification of the polymer by adding the silane groups mainly in a process of free radical grafting. Such compounds and comonomers containing silane groups are well known in the field and, for example, commercially available. The hydrolyzable silane groups are typically then cross-linked by hydrolysis and subsequent condensation in the presence of a silanol condensation catalyst and trace water in a manner known in the art. The silane crosslinking technique is also well known in the art.
    [00066] Preferably, the crosslinkable semiconductor composition layer comprises crosslinking agent (s), preferably free radical generating agent, more preferably peroxide. Consequently, the crosslinking of at least the insulation layer, and optionally, and preferably, of at least one semiconductor layer, is preferably carried out by radical reaction
    Petition 870190105690, of 10/18/2019, p. 26/51
    21/35 free using one or more free radical generating agents, preferably peroxide (s).
    [00067] When peroxide is used as a crosslinking agent, then the crosslinking agent is preferably used in an amount less than 10% by weight, more preferably in an amount between 0.1 to 8% by weight, even more preferably in an amount of 0.2 to 3% by weight and even more preferably in an amount of 0.3 to 2.5% by weight with respect to the total weight of the composition to be cross-linked.
    [00068] Non-limiting examples of peroxidic crosslinking agents are organic peroxides, such as di-tert-amylperoxide, 2,5di (tert-butylperoxy) -2,5-dimethyl-3-hexine, 2,5-di (tert -butylperoxy) -2,5dimethylexane, tert-butylcumylperoxide, di (tert-butyl) peroxide, dicumylperoxide, butyl-4,4-bis (tert-butylperoxy) -valerate, 1,1-bis (tert-butylperoxy) -
    3,3,5-trimethylcyclohexane, tert-butylperoxybenzoate, dibenzoylperoxide, bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl) -2,5-di (benzoylperoxy) hexane, 1,1 -di (tert-butylperoxy) cyclohexane , 1,1 -di (tert-amylperoxy) - cyclohexane, or any mixture thereof. Preferably, the peroxide is selected from 2,5-di (tert-butylperoxy) -2,5-dimethylexane, di (tertbutylperoxyisopropyl) benzene, dicumylperoxide, tert-butylcumylperoxide, di (tert-butyl) peroxide, or mixtures thereof.
    [00069] In another embodiment of the present invention the semiconductor polyolefin composition may also contain other additives, such as antioxidant (s), stabilizer (s), water-free retardant additive (s), processing aid , burn retardant, charge (s), metal deactivator, crosslinker, flame retardant additive, acid or ion recoverer, additional inorganic charge, voltage stabilizer or any mixture thereof. Additives are typical use in concentrations of 0.01% by weight to 10% by weight.
    Petition 870190105690, of 10/18/2019, p. 27/51
    22/35 [00070] As non-limiting examples of antioxidants, for example, sterically hindered or semi-hindered phenols, aromatic amines, sterically hindered aliphatic amines, organic phosphites, or phosphonites, thio compounds, and mixtures thereof.
    [00071] Preferably, the antioxidant is selected from the group of diphenyl amines and diphenyl sulfides. The phenyl substituents on these compounds can be substituted with other groups such as alkyl, alkylaryl, arylalkyl, or hydroxy groups.
    [00072] Preferably, the phenyl groups of diphenyl amines and diphenyl sulfides are substituted with tert-butyl groups, preferably at the target or position, which may contain other substituents such as phenyl groups.
    [00073] More preferred, the antioxidant is selected from the group of 4,4'-bis (1,1'dimethylbenzyl) diphenylamine, para-oriented styrene diphenyl amines, 6,6-di-terc.-butyl-2,2'- thiodi-p-cresol, tris (2-terc.-butyl-4-thio- (2'methyl-4-hydroxy-5'-terc.-butyl) phenyl-5-methyl) phenylphosphide, 2,2,4- polymerized trimethyl-1,2-dihydroquinoline, or derivatives thereof. Certainly, not only one of the antioxidants described above can be used, but also any mixture of them.
    [00074] The amount of an antioxidant is preferably from 0.005 to 2.5% by weight, based on the weight of the semiconductor composition. Antioxidants are preferably added in an amount of 0.005 to 2% by weight, more preferably 0.01 to 1.5% by weight, even more preferably 0.04 to 1.2% by weight, based on the weight of the semiconductor composition. . In another preferred embodiment, the semiconductor composition may comprise free radical generation agents, one or more antioxidants and one or more burn retardants.
    [00075] Burn retardant (SR) is a type of additive well
    Petition 870190105690, of 10/18/2019, p. 28/51
    23/35 known in the field and may this is to prevent premature crosslinking. As also known, the SR can also contribute to the level of establishment of the polymer composition. As examples of burn retardants are allyl compounds, such as aromatic alpha-methyl alkenyl monomer dimers, preferably 2,4-diphenyl-4-methyl-1-pentene, substituted or unsubstituted diphenylethylenes, quinone derivatives hydroquinone, ethers and esters containing monofunctional vinyl, monocyclic hydrocarbons having at least two or more double bonds, or mixtures thereof, may be mentioned. Preferably, the amount of a burn retardant is within the range of 0.005 to 2.0% by weight, more preferably within the range of 0.005 to 1.5% by weight, based on the weight of the semiconductor composition. Other preferred ranges are, for example, 0.01 to 0.8% by weight, 0.03 to 0.75% by weight, 0.03 to 0.70% by weight, or 0.04 to 0.60 % by weight, based on the weight of the semiconductor composition. A preferred SR added to the semiconductor composition is 2,4-diphenyl-4-methyl-1-pentene.
    [00076] Examples of processing aids include, however, are not limited to metal salts of carboxylic acids such as zinc stearate or calcium stearate; fatty acids; fatty amides; polyethylene wax; copolymers of ethylene oxide and propylene oxide; oil waxes; nonionic surfactants and polysiloxane. [00077] Non-limiting examples of additional loads are precipitated silicate and silica clays and; fumed silica calcium carbonate.
    [00078] It is intended throughout the present description that the term composition encompasses mixing the material according to standard methods for those skilled in the art. Non-limiting examples of compositing equipment are continuous double or single helix mixers such as Farell®, Werner and Pfleiderer®, Ko
    Petition 870190105690, of 10/18/2019, p. 29/51
    24/35 belco Bollling® and Buss®, or internal batch mixers, such as Brabender® or Banbury®.
    [00079] Any suitable process known in the art can be used for the preparation of the semiconductor polyolefin compositions of the present invention such as dry mix, solution mix, solution shear mix, melt mix, extrusion, etc.
    [00080] The present invention is also directed to a process for producing the preferred inventive semiconductor polyolefin composition, comprising premixing the graphene nanoplatelets and the solid conductive filler.
    [00081] Premix as used here should indicate that the mixing occurs before the resulting mixture is contacted and mixed with the olefin polymer base resin.
    [00082] As mentioned above, the semiconductor polyolefin composition of the present invention is highly useful in a wide variety of cable and wire applications. Especially it can be incorporated in an electric power cable, particularly in a semiconductor layer of the cable. A power cable is defined to be a cable that transfers energy at any voltage, typically operating at voltages greater than 1 kV. The voltage applied to the power cable can be alternating (AC), direct (DC), or transient (impulse). Electric power cables, especially medium voltage, high voltage and extra high voltage cables, typically comprise two semiconductor layers and an insulating layer. The term semiconductor refers to the intermediate electrical conductivity between that of insulating materials and conducting materials. A typical range of electrical conductivity for semiconductors is in the range of 10 9 to 10+ 3 S / cm (see, for example, McGraw-Hill Dictionary of scientific and technical terms), corresponding to the electrical resistivity between
    Petition 870190105690, of 10/18/2019, p. 30/51
    25/35
    10 9 to 10 + 3 ohm cm. Therefore, the term semiconductor excludes insulating materials. Likewise, the present semiconductor polyolefin composition and its ingredients exclude any application for insulating compositions or insulating layers in a power cable.
    [00083] The cable preferably comprises one or more conductors surrounded by at least one semiconductor layer and an insulating layer, in that order. More preferably, the cable comprises a conductor surrounded by an inner semiconductor layer, an insulating layer and optionally, and preferably, an outer semiconductor layer, in that order, as defined above. More preferably, at least the inner semiconductor layer comprises the semiconductor composition. Preferably also the outer semiconductor layer comprises the semiconductor composition.
    [00084] In a preferred embodiment at least the inner semiconductor layer of the cable is crosslinkable. The outer semiconductor layer of the cable can be crosslinkable or non-crosslinkable, depending on the final application. In addition, the outer semiconductor layer of the cable, if present, can be attached or removable, the terms of which have a well-known meaning in the field. The semiconductor composition of the cable may comprise other components, such as also polymer components and / or one or more additives.
    [00085] It is evident to a skilled person that the cable may optionally comprise one or more other layers comprising one or more screens, a jacket layer or another protective layer, the layers of which are conventionally used in the wire and cable field.
    [00086] The preferred cable is preferably an alternating current (AC) or direct current (DC) power cable, more preferably a medium voltage (MV), high voltage (HV) power cable or a
    Petition 870190105690, of 10/18/2019, p. 31/51
    26/35 extra-high voltage (EHV). It is clear that the following modalities, subgroups and other preferable properties of the polymer compositions, and components thereof, and of the cable layers are generalizable and independent definitions that can be used in any combination to also define the cable.
    [00087] The polyolefin composition of the present invention is highly suitable for power cables, especially for power cables operating at voltages greater than 6 kV to 36 kV (medium voltage (MV) cables) and at higher voltages than 36 kV, known as high voltage (HV) cables and extra high voltage (EHV) cables, whose EHV cables operate, well known at very high voltages. The terms have well-known meanings and indicate the operational level of such cables. Combined with good electrical conductivity, the semiconductor composition also has superior surface smoothness and high processability.
    [00088] The invention also provides a process for producing a cable, preferably a crosslinkable power cable, as defined above or in the claims, comprising the steps of applying to a conductor, preferably by (co) extrusion, at least one semiconductor layer comprising the semiconductor polyolefin composition of the present invention. In addition, the layers can be applied in the same coextrusion step or additional coextrusion step.
    Examples
    1. Measurement Methods (a) Fusion Flow Rate [00089] The MFR2 was measured with 2.16 kg of load at 190 ° C for polyethylene and 230 ° C for polypropylene according to ISO 1 133.
    (b) Volume resistivity
    Petition 870190105690, of 10/18/2019, p. 32/51
    27/35 [00090] For the measurement of volume resistivity, the 2 mm thick plates were pressed at 150 ° C for two minutes. The plates were cooled to room temperature. The plates were placed between two metal electrodes and the plates heated to 120 ° C for 30 minutes to anneal the sample and ensure good contact between the compound and the electrodes. The compounds were slowly cooled to room temperature, roughly to 22 ° C. Resistance R in ohm is measured using an ohm meter. Area A is calculated as Α = π (d / 2) 2 where d is the diameter of the circular electrodes in cm. L is the thickness in cm of the plates after annealing. All distances are measured by gauges or micrometer screws. Volume resistance VR is calculated as VR = RxA / L.
    (c) Temperature Resistivity of Volume Resistivity [00091] Volume resistivity was measured on plates with a thickness between 1 to 3 mm and a diameter of 20 to 50 mm. The plates were produced by applying pressure to the sample at temperatures ranging from 150 to 180 ° C. Volume resistance was measured with a broadband dielectric spectrometer (Novocontrol, Alpha) at a frequency of 50 Hz using stainless steel electrodes. The rate of heating and cooling was 5 K / minute (GNP composition) or 10 K / minute (CB compositions). Before the thermal cycle, the materials were annealed at or above 120 ° C for 10 minutes to remove the influence of thermal history. In the thermal scan, the additional annealing stages were carried out for 10 or 5 minutes for the sample in Example 3 and the sample in Comparative Example 4. Annealing is done by heating a sample and keeping it at this increased temperature for an extended period of time. The temperature is chosen so that it is above the melting temperature of the resin. The time is selected to remove which
    Petition 870190105690, of 10/18/2019, p. 33/51
    28/35 wants thermal history. The treatment removes internal tension and all parameters that have been affected due to manufacture.
    [00092] The volume resistance VR is obtained directly from the instrument and calculated as VR = RxA ZL, where L is the thickness of the plates and area A is calculated as Α = π (d / 2) 2 , where d is the diameter circular electrodes. All distances used in the calculations are measured by gauges or micrometer screws.
    (d) Surface roughness [00093] The surface roughness of the material was determined by investigations with optical microscopy of the surface of extruded filaments under conditions applied in MFR experiments (ISO 1 133, with 2.16 kg load at 190 ° C) . The filament surface was recorded with an optical camera focused on the filament profile. The typical profile length investigated was 2.5 mm and the optical magnification 50 times. The distances were calibrated with special objective glass with millimeter markers. The registered profile was analyzed and the position of the border extracted. This can, for example, be done with edge detection routines, for example, made available by MatLab®. The curvature or mixture of long strands of the filaments was corrected by adjusting the least squares curve with a polynomial of order 2. The surface roughness was then calculated as the R_RMS calculated as
    Equation 1
    R_RMS
    [00094] Here Ay is the deviation in micrometers between the registered edge and the polynomial, i is the index of different pixels along the profile. For each material at least 8 different photos were recorded and analyzed. The standard deviation of the surface roughness index obtained, R_RMS, was calculated.
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    29/35
    2. Materials
    Graphene Nanoplates. GNP [00095] xGNP®, commercially available from XG Science. The density of xGNP is about 2.0 g / cm 3 and the thickness of the platelet is in the range of 8 to 13 nanometers. The average lateral size (diameter) is about 5 micrometers. The BET data shown in the xGnP surface area has reached more than 100 m 2 / g.
    Carbon black [00096] Elftex® 254, commercially available from Cabot Corporation, Leuwen, Belgium with the following properties :.
    • Number of iodine measured by ASTM D1510 <180 m / g • Particle size measured by ASTM D3849, procedure D <25 nm • Ash content measured by ASTM D1506 <0.1% • Toluene extract measured by ASTM D4527 <0 , 03% Expanded Graphite [00097] TIMREX® BNB90®, commercially available from
    Timcal Graphite and Carbon. This work has a particle size distribution with a D90 less than 100 pm. The surface areas are characterized with BET = 28 m 2 / g and oil absorption number of 150 ml / 100 g.
    EVA [00098] Escorene ® 783, commercially available from
    ExxonMobile [00099] The vinyl acetate content of the material was 33% and the MFR2 = 43 g / 10min at 190 ° C and 2.16 kg.
    [000100] The materials were produced by mixing the polymer with the conductive filler using a Brabender mixer. For all compounds the conductive charge constitutes 10 percent based on the weight shown in the table below. The base resin for materials
    Petition 870190105690, of 10/18/2019, p. 35/51
    30/35 in Table 1 is ethylene vinyl acetate (ESCORENE® 783) with a vinyl acetate content of 33% by weight and MFR2 of 43 g / 10 minutes (EVA1). For Comparative Example 4, an ethylene vinyl acetate (ESCORENE ® 783) with a vinyl acetate content of 20% by weight and MFR2 of 20 g / 10 minutes (EVA2) and for Comparative Example 5, a vinyl acetate ethylene (ESCORENE ® 783) with a 9% weight and vinyl acetate content and 9 g / 10 minutes MFR2 (EVA3) was used. The GNP used was obtained from XG Science (xGNP®) with a typical thickness in the range of 8 to 13 nanometers and a diameter of about 5 micrometers. The expanded graphite was TIMREX BNB90. The carbon black was CABOT's Elftex 254.
    [000101] The compounds were produced in general, according to the description of Kalaitzidou and others. Composites Science and Technology 67 (2007) 2045. The following processing scheme has been adopted.
    [000102] The base resin was cooled with liquid nitrogen and ground to a powder. The appropriate amount of GNP or carbon black was dispersed in isopropanol in a glass bottle, with approximately 10 times more isopropanol by weight. For composition with a combination of carbon black and GNP and / or carbon black it was dispersed in the isopropanol solution after GNP. The isopropanol solution with the GNP and / or carbon black was placed in an ultrasound bath for 30 minutes at room temperature. The base resin was dispersed in the isopropanol solution with the GNP and / or carbon black to make a mixture. The suspension was placed in an ultrasound bath for another 30 minutes. Excessive isopropanol was evaporated by storage at room temperature for a few days. The suspension was composed in a Brabender batch mixer preheated to 190 ° C and mixed at 50 revolutions per minute (RPM) for 10 minutes.
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    31/35
    Table 1
    Example No.1 Example No. 2 Comparative Example No. 1 Comparative Example No. 1 Comparative Example No.1 EVA1 % by weight 90 90 90 90 100 xGNP % by weight 10 8 Expanded graphite % by weight 10 Carbon Black % by weight210 MFR2 (190 o C / 2.16 kg) g / 10 min 15.12 21.68 12.05 34.83 43 VR ohm cm 9.5x106 2.5 x 10 4 1.7 x 10 5 8.3 x 10 9 > 1 x 10 3 R RMS pm 79.7 +6.2 57.1 +13.4 123.6 + 14.7 66.5 +22.8 AT MFR2 (Composition) / MFR2 (base resin)0.35 0.50 0.28 0.81 1.00
    [000103] The measurements show that with the expanded graphite the surface is very rough, R_RMS above 100 micrometers, and unsuitable for cable applications. Example 1 containing 10% by weight of GNP has excellent surface smoothness, while the viscosity and volume resistivity are in a range suitable for semiconductor applications. In contrast, Comparative Example 2 shows that with 10% by weight of carbon black the resistivity is very high, i.e. the material is not semiconductor. For all other compositions the volume resistivity is in the semiconductor range. The lower volume resistivity is observed by mixing GNP and carbon black. The measurements also show that the lowest MFR values are obtained with expanded graphite, thereby leading to unacceptable fluidity and also the smoothness of the surface was unacceptable for cable applications. With GNP or carbon black the flow capacity is sufficiently high. O
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    32/35
    FR2 of pure EVA is 43 g / 10minutes. To summarize the measurements show that semiconductor compositions based on GNP determine higher surface smoothness and higher MFR (lower viscosity) as well as low volume resistivity. Especially beneficial is the combination of GNP and carbon black.
    [000104] In other series of experiments the temperature dependence of the volume resistivity and the self-healing effect under annealing were examined. The compositions according to the following Table 2 were prepared and tested. The compositions according to Example 3, Comparative Example 4 and Comparative Example 5 were prepared according to the procedures described for the compositions shown in Table 1 above.
    Table 2
    Ex. 3 Comparative Example 4 Ex. Comparisonasset 5 EVA1 SCORENO 783(MFR2 = 43, 33% VA) 90 EVA2 MFR2 = 20, VA = 20%84.2EVA3 MFR2 = 9, VA = 9% 63.2 GNP xGNP (XG Science) 10 CB Conductex 705115 36 TO TMQ0.8 0.8 VRpico / VRRT (heating)14 43,300 230 VRpico / VR50oC (cooling)1.2 75 20
    [000105] Figure 5 and figure 6 show volume resistivity as a function of temperature for the three compositions under heating and cooling, respectively. Figure 5 shows that the VR temperature dependence for inventive Example 3 comprising GNP is much less pronounced than for Comparative Examples comprising carbon black. In the Compa Examples
    Petition 870190105690, of 10/18/2019, p. 38/51
    33/35 ratives 4 and 5 two different CB contents (36% by weight and 15% by weight) were used. It can be observed that the ratio of maximum VR to VR at room temperature (23 o C) is approximately 230 and 43300 in 36% by weight and 15% by weight of CB loads, respectively, at the same time as the corresponding value for the GNP composite is 14. This shows that VR of the GNP composition has much less pronounced temperature dependence than CB compositions. This is a distinct advantage for semiconductor polymer compositions in power cable applications since the semiconductor composition and the layer will have less temperature variation when operated at different force loads, which successively result in the development of increased temperature variation. The lower temperature dependence implies that a higher VR can be accepted at room temperature and the total fill load can thus be reduced.
    [000106] The difference between GNP and CB compositions is even more pronounced when the cooling cycle is considered, as shown in figure 6. The GNP composition (Example 3) reveals an almost perfect flat line whereas CB compositions ( Comparative Examples 4 and 5) have similar performance as under heating with a pronounced peak, although the position of the peak is slightly changed at lower temperatures. The observed values for VRpico / VR50 ° c under cooling are 1.2, for Example 3, 75 for Comparative Example 4 and 20 for Comparative Example 5, respectively.
    [000107] The absence of a peak for the GNP composition, therefore, implies that the percolation pathways in this system are not disturbed by the crystallization of the polymer, or in other words, the polymer crystallizes in domains around the GNP.
    [000108] A new additional discovery with the composition of po
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    34/35 inventive semiconductor polymers is the reduction of VR under annealing at temperatures below melting temperatures. For the compositions according to Comparative Examples 4 and 5, the VR remains almost unchanged when the temperature is kept constant as shown in figure 7. This is in contrast to the inventive Example 3 where a reduction of VR too much than 25% is observed when annealed for 5 minutes. In addition, prolonging annealing also appears to reduce VR. This is a major beneficial feature for power cable semiconductor compositions since one of the restraining factors is that thermal cycling and prolonged annealing results in deteriorating VR performance for semiconductor polymer compositions including carbon black so that the GNP compositions of the invention achieve substantial advancement in VR performance in the long run, if the compositions are used in semiconductor layers for power cables.
    [000109] Thus, the semiconductor polyolefin composition of the present invention not only provides a substantial decrease in surface roughness and volume resistivity, but also provides a substantial increase in processability and fluidity which is highly desirable for the manufacture of semiconductor layers in power cables. In addition, by the inventive combination of graphene and carbon black nanoplatforms in the semiconductor composition, not only can the above effects be achieved, but the process costs can be significantly reduced. The partial substitution of graphene nanoplatts, which are quite expensive, with carbon black leads to savings while the partial replacement of carbon black with graphene nanoplets determines synergistic effects in relation to the reduction of surface roughness, decreased conductivity and simultaneous fluidity of
    Petition 870190105690, of 10/18/2019, p. 40/51
    35/35 inventive composition. In addition, the temperature dependence of the volume resistivity can be reduced and a self-healing effect can be seen in long-term VR performance over conventional carbon black loaded semiconductor compositions.
    权利要求:
    Claims (14)
    [1]
    1. Power cable, characterized by the fact that it comprises a semiconductor polyolefin composition that comprises:
    (a) an olefin-based polymer resin, and (b) graphene nanoplatforms in which the graphene nanoplates (b) have an average thickness in the range of 1 nm to 50 nm and a side diameter of 200 pm or less, both measured with atomic force microscopy (AFM).
    [2]
    2. Power cable according to claim 1, characterized by the fact that the semiconductor polyolefin composition further comprises:
    (c) a solid conductive charge other than (b).
    [3]
    3. Power cable according to claim 1 or 2, characterized by the fact that the average thickness of the graphene nanoplatelets (b) is in the range of 1 nm to 40 nm.
    [4]
    Power cable according to any one of claims 1 to 3, characterized in that the graphene nanoplatelets (b) have an aspect ratio of diameter to thickness that is 50 or more, measured by atomic force microscopy .
    [5]
    Power cable according to any one of claims 1 to 4, characterized in that the graphene nanoplatelets (b) are contained in the semiconductor polyolefin composition in the range of 2 to 20% by weight, based on the total weight of the polyolefin composition.
    [6]
    Power cable according to any one of claims 2 to 5, characterized in that the solid conductive charge (c) is carbon black.
    [7]
    7. Power cable according to claim 6, characterized by the fact that said carbon black fills at least
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    2/3 one of the following requirements:
    (a) an iodine number of at least 30 mg / g, measured according to ASTM D 1510, (b) a DBP oil absorption number of at least 30 ml / 100 g, measured according to ASTM D 2414 , (c) a BET nitrogen surface area of at least 30 m 2 / g, measured according to ASTM D 3037, (d) a statistical surface area (STSA) of at least 30 m 2 / g measured according to with ASTM D5816.
    [8]
    Power cable according to any one of claims 2 to 7, characterized in that the solid conductive charge (c) is contained in the semiconductor polyolefin composition with a fraction of 5 to 95% by weight, in relation to weight graphene nanoplatelets (b).
    [9]
    Power cable according to any one of claims 1 to 8, characterized in that the olefin-based polymer resin (a) comprises an ethylene homo- or copolymer or a propylene homo- or copolymer.
    [10]
    Power cable according to any one of claims 1 to 9, characterized in that the olefin-based polymer resin (a) comprises an ethylene copolymer with at least one comonomer selected from unsaturated esters, preferably esters of vinyl, esters of acrylic acid or methacrylic acid, more preferably the at least one comonomer is selected from methyl acrylate, ethyl acrylate or butyl acrylate, more preferably with the quantity of acrylate comonomer units from 1 to 15 mol% with respect to the total amount of monomers in the polymeric part of the composition.
    [11]
    Power cable according to any one of claims 1 to 10, characterized in that the polio composition
    Petition 870190105690, of 10/18/2019, p. 43/51
    3/3 semiconductor lefin has a ratio of MFR2 of the polyolefin composition to MFR2 of the olefin polymer base resin of 0.30 or more, where MFR2 is measured at a load of 2.16 kg according to ISO 1133, at a temperature of 190 ° C for polyethylene and at a temperature of 230 ° C for polypropylene.
    [12]
    Power cable according to any one of claims 1 to 11, characterized in that the surface roughness of the semiconductor polyolefin composition obtained by R_RMS, measured in the extruded samples, is 100 micrometers or less.
    [13]
    Power cable according to any one of claims 1 to 12, characterized in that it comprises a semiconductor layer comprising the semiconductor polyolefin composition, as defined in any one of claims 1 to
    12.
    [14]
    14. Use of a semiconductor polyolefin composition that comprises:
    (a) an olefin-based polymer resin, and (b) graphene nanoplugs, characterized by the fact that it is in a semiconductor layer of a power cable, in which the graphene nanoplates (b) have an average thickness in the range from 1 nm to 50 nm and a lateral diameter of 200 pm or less, both measured with atomic force microscopy (AFM).
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    同族专利:
    公开号 | 公开日
    CN103097444B|2015-09-09|
    RU2543178C2|2015-02-27|
    RU2012136597A|2014-03-10|
    MX2012010768A|2012-10-15|
    KR101426900B1|2014-08-05|
    EP2556111A1|2013-02-13|
    CN103097444A|2013-05-08|
    EP2374842B2|2019-09-18|
    EP2374842A1|2011-10-12|
    BR112012025245A2|2016-06-21|
    US9543056B2|2017-01-10|
    US20130037759A1|2013-02-14|
    EP2374842B1|2013-07-10|
    KR20120128153A|2012-11-26|
    WO2011124360A1|2011-10-13|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2019-10-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-12-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/04/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP10003716.7A|EP2374842B2|2010-04-06|2010-04-06|Semiconductive polyolefin composition comprising conductive filler|
    PCT/EP2011/001686|WO2011124360A1|2010-04-06|2011-04-05|Semiconductive polyolefin composition comprising conductive filler|
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