Multiphase conductive polymer composite composition

Abstract

The composition has (A) a γ value of 1 mN / m or more and 5 mN / m or less. P (B) an ethylene / unsaturated ester copolymer having a γ of 0 mN / m or more and less than 1 mN / m; P and (C) a non-polar polymer having a γ of greater than 5 mN / m, and selected from the group consisting of polyethylene homopolymer, silane-functionalized polyethylene homopolymer, ethylene / alpha-olefin copolymer, and silane-functionalized ethylene / alpha-olefin copolymer; P and (D) at least two additional polymers selected from the group consisting of an ethylene / unsaturated ester copolymer having a carboxylic acid group selected from the group consisting of EPDM copolymers, and a three-phase polymer composite comprising a conductive filler dispersed in only one of (A) and the at least two additional polymers, wherein (i) one of the at least two additional polymers is selected from (B) and the other is selected from (C) or (D), or (ii) one of the at least two additional polymers is selected from (C) and the other is selected from (B) or (D). [Selected Figure] Figure 1

Description

[Technical field]

[0001] Generally, a single polymer system may have a molecular weight of, for example, 10 -9 ~10 -3 To achieve significant electrical conductivity on the order of S / cm, substantial concentrations of conductive fillers are required. Such substantial concentrations of conductive fillers increase the melt viscosity of the material while also decreasing the mechanical properties of the material. One approach to increase the electrical conductivity of composites at low filler concentrations, thereby minimizing the detrimental effects on the mechanical and rheological properties, is to use multiphase polymer blends that can lower the percolation threshold. In the case of two-component polymer blends, some studies have found that the percolation threshold can be reduced using two-phase polymer blends in which the conductive filler is incorporated into an immiscible polymer blend and is governed by the conductive filler-rich phase and the continuity of this phase within the polymer blend.

[0002] Ternary polymer blends, i.e., three-component polymer blends, in combination with conductive fillers, such as carbon black, have also been shown to reduce the percolation threshold and achieve electrical conductivity in several different polymer systems. However, such ternary polymer blends still exhibit significant brittleness. In some applications, brittleness can be improved at the expense of an increased percolation threshold.

[0003] There is a need for polymer composite compositions that use crosslinkable polymers and that exhibit improved, i.e., lower permeation thresholds and improved, i.e., lower brittleness. Additionally, there is a need for such composite compositions that exhibit improved, i.e., lower melting points and glass transition temperatures, and improved, i.e., increased flexibility, particularly for cable applications. Summary of the Invention

[0004] The present disclosure provides a composition comprising the following components: (A) The polar component of surface tension between 1 milliNewton per meter (mN / m) and 5 mN / m (γP ) and at least one copolymer of ethylene and an unsaturated ester having the formula: (B) Polar component of surface tension from 0 mN / m to less than 1 mN / m (γ P ) at least one non-polar polymer selected from the group consisting of polyethylene homopolymer, silane-functionalized polyethylene homopolymer, ethylene / alpha-olefin copolymer, and silane-functionalized ethylene / alpha-olefin copolymer; (C) Polar component of surface tension above 5 mN / m (γ P ) At least one copolymer of ethylene and an unsaturated ester having the formula: (D) at least two additional polymers selected from the group consisting of at least one ethylene propylene diene monomer copolymer; A composition comprising a three-phase polymer composite comprising component (A) and a conductive filler dispersed in only one of at least two additional polymers, (i) a first polymer of the at least two additional polymers is selected from (B) and a second polymer of the at least two additional polymers is selected from (C) or (D); or (ii) a first polymer of the at least two additional polymers is selected from (C) and a second polymer of the at least two additional polymers is selected from (B) or (D).

[0005] In another embodiment, the present disclosure provides a cable comprising a conductor; an inner semiconducting layer covering at least a portion of the conductor; an insulating layer covering at least a portion of the inner semiconducting layer; and an outer semiconducting layer covering at least a portion of the insulating layer, wherein at least one of the inner and outer semiconducting layers comprises the following composition: (A) The polar component of surface tension between 1 milliNewton per meter (mN / m) and 5 mN / m (γ P )and at least one copolymer of ethylene and an unsaturated ester having the formula: (B) Surface tension between 0 mN / m and less than 1 mN / m of Polar Components (γ P ) at least one non-polar polymer selected from the group consisting of polyethylene homopolymer, silane-functionalized polyethylene homopolymer, ethylene / alpha-olefin copolymer, and silane-functionalized ethylene / alpha-olefin copolymer; (C) Surface tension greater than 5mN / m of Polar Components (γ P ) At least one copolymer of ethylene and an unsaturated ester having the formula: (D) at least two additional polymers selected from the group consisting of at least one ethylene propylene diene monomer copolymer; a three-phase polymer composite comprising component (A) and a conductive filler dispersed in only one of the at least two additional polymers; (i) a first polymer of the at least two additional polymers is selected from (B) and a second polymer of the at least two additional polymers is selected from (C) or (D); or (ii) a first polymer of the at least two additional polymers is selected from (C) and a second polymer of the at least two additional polymers is selected from (B) or (D). [Brief description of the drawings]

[0006] [Figure 1] 1 is a plot of resistivity vs. date for comparative examples and inventive examples showing the percolation limit; DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] In one embodiment, the present disclosure provides a composition comprising: (A) a surface tension of 1 milliNewton per meter (mN / m) or more and 5 mN / m or less; of Polar Components (γ P ) (B) at least one copolymer of ethylene and an unsaturated ester having a surface tension of from 0 mN / m to less than 1 mN / m; of Polar Components (γ P ) and (C) at least one non-polar polymer selected from the group consisting of polyethylene homopolymer, silane-functionalized polyethylene homopolymer, ethylene / alpha-olefin copolymer, and silane-functionalized ethylene / alpha-olefin copolymer; and (D) a surface tension of greater than 5 mN / m. of Polar Components (γ P ) and (D) at least two additional polymers selected from the group consisting of at least one copolymer of ethylene and an unsaturated ester having a structure represented by the formula:

[0008] Ingredient A In one embodiment, the ternary polymer composite has (A) a surface tension of 1 mN / m or more and 5 mN / m or less. of Polar Components (γ P ) The composition comprises at least one copolymer of ethylene and an unsaturated ester ("component (A)") having the formula:

[0009] In one embodiment, the unsaturated ester is an alkyl acrylate or alkyl methacrylate. Preferably, the alkyl is a C1-C8 alkyl, more preferably a C1-C4 alkyl. Preferred carboxylates are those containing 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms.

[0010] Examples of acrylic and methacrylic esters are lauryl methacrylate, myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, 3-methacryloxypropyl trimethoxysilane, 30-methacryloxypropyl triethoxysilane, cyclohexyl methacrylate, n-hexyl methacrylate, isodecyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, octyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl methacrylate, isooctyl methacrylate, isooctyl methacrylate, oleyl methacrylate, ethyl acrylate, methyl acrylate, t-butyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. Methyl acrylate, ethyl acrylate, and n- or t-butyl acrylate are preferred.

[0011] In one embodiment, the amount of ester comonomer in component (A) is from 2 wt.% or more, or 10 wt.% or more, or 15 wt.% or more, to 55 wt.% or less, or 30 wt.% or less.

[0012] In one embodiment, the density of component (A) is from 0.900 g / cc or more, or 0.920 g / cc or more, to 0.990 g / cc or less, or 0.970 g / cc or less.

[0013] In one embodiment, the melt index of component (A) is from 0.1 g / 10 min or more, or 1 g / 10 min or more, or 5 g / 10 min or more, to 100 g / 10 min or less, or 50 g / 10 min or less, or 21 g / 10 min or less.

[0014] In one embodiment, the melting point of component (A) is less than 166°C.

[0015] In one embodiment, component (A) has a glass transition temperature (Tg) of less than 25°C.

[0016] Preferably, component (A) is selected from the group consisting of ethylene-ethyl acrylate, ethylene-methyl acrylate, ethylene-butyl acrylate, and combinations thereof.

[0017] In one embodiment, component (A) has a surface tension of 1 milliNewton per meter (mN / m) or more and 5 mN / m or less. of Polar Components (γ P ) The copolymer may be a mixture of two or more copolymers of ethylene and an unsaturated ester having the formula:

[0018] In one embodiment, component (A) is present in the ternary polymer composite in an amount from greater than 0 volume percent, or 1 volume percent or more, or 2.5 volume percent or more, or 7.5 volume percent or more, or 15 volume percent or more, to 40 volume percent or less, or 30 volume percent or less, or 25 volume percent or less, based on the total volume of the composite.

[0019] Component B In an embodiment, the ternary polymer composite has (B) a surface tension of 0 mN / m or more and less than 1 mN / m. of Polar Components (γ P ) and comprises at least one non-polar polymer (“Component (B)”) selected from the group consisting of polyethylene homopolymer, silane-functionalized polyethylene homopolymer, ethylene / alpha-olefin copolymer, and silane-functionalized ethylene / alpha-olefin copolymer.

[0020] In one embodiment, component (B) is a polyethylene homopolymer. Preferably, the polyethylene homopolymer is low density polyethylene (LDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE) or high density polyethylene (HDPE).

[0021] LDPE is known in the art and is commercially available. Typically, LDPE has a density of greater than or equal to 0.910 g / cc and less than or equal to 0.940 g / cc.

[0022] VLDPE is known in the art and commercially available. Typically, VLDPE has a density of greater than or equal to 0.860 g / cc and less than or equal to 0.915 g / cc.

[0023] LLDPE is known in the art and commercially available. Typically, LLDPE has a density of greater than or equal to 0.916 g / cc and less than or equal to 0.925 g / cc.

[0024] MDPE is known in the art and commercially available. Typically, MDPE has a density of greater than or equal to 0.925 g / cc and less than or equal to 0.940.

[0025] HDPE is known in the art and is commercially available. Typically, HDPE has a density of not less than 0.940 g / cc and not more than 0.970 g / cc.

[0026] In one embodiment, component (B) is an ethylene / alpha-olefin copolymer.

[0027] Alpha-olefins are hydrocarbon or substituted hydrocarbon molecules (i.e., hydrocarbon molecules containing one or more atoms other than hydrogen and carbon, such as halogens, oxygen, nitrogen, etc.) that (i) contain only one ethylenic unsaturation, which is located between a first and a second carbon atom, and (ii) contain at least three carbon atoms, preferably 3 to 20 carbon atoms, in some cases preferably 4 to 10 carbon atoms, and in other cases preferably 4 to 8 carbon atoms. Non-limiting examples of α-olefins from which copolymers may be prepared include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-dodecene, and mixtures of two or more of these monomers.

[0028] In one embodiment, the ethylene / alpha-olefin copolymer is preferably an ethylene / propylene, ethylene / 1-butene, ethylene / 1-hexene, or ethylene / 1-octene copolymer, more preferably an ethylene / propylene, ethylene / 1-butene, ethylene / 1-hexene, or ethylene / 1-octene copolymer.

[0029] In one embodiment, ethylene / alpha-olefins suitable for use in the present disclosure contain greater than 50 mole % polymerized ethylene monomer, based on the total amount of polymerizable monomers, and at least one alpha-olefin comonomer.

[0030] In one embodiment, the polyethylene homopolymer or ethylene / alpha-olefin copolymer is functionalized with silane. Such silane-functionalized polymers can be made by copolymerization with vinylsilane monomers or by one of many methods for grafting silane-containing molecules to the backbone of polymeric polymers. Examples of such techniques are disclosed in U.S. Patent Nos. 3,646,155; 6,420,485; 6,331,597; 3,225,018; 4,574,133; or 6,048,935, all of which are incorporated herein by reference. Examples of silane compounds that can be used to add silane functional groups to polyethylene homopolymer or ethylene / alpha-olefin copolymer include, but are not limited to, vinyl silanes, such as vinyl trialkoxysilanes. Typically, the amount of silane is generally greater than 0% by weight and less than or equal to 5% by weight based on the total weight of polyethylene homopolymer or ethylene / alpha-olefin copolymer.

[0031] In one embodiment, component (B) is a silane-functionalized polyethylene homopolymer or a silane-functionalized ethylene / alpha-olefin copolymer. In one embodiment, component (B) is a silane-functionalized polyethylene homopolymer or a silane-functionalized ethylene / alpha-olefin copolymer, which is crosslinked.

[0032] In one embodiment, component (B) is a silane-grafted polyethylene homopolymer or a silane-grafted ethylene / alpha-olefin copolymer. In one embodiment, component (B) is a silane-grafted polyethylene homopolymer or a silane-grafted ethylene / alpha-olefin copolymer, which is crosslinked.

[0033] Preferably, component (B) is selected from the group consisting of polyethylene homopolymer, silane-functionalized polyethylene homopolymer, and combinations thereof. More preferably, component (B) is selected from the group consisting of LDPE, silane-functionalized LDPE, and combinations thereof.

[0034] In one embodiment, component (B) has a surface tension of less than 1 mN / m, or less than or equal to 0.5 mN / m, or less than 0.5 mN / m, or 0.0 mN / m. of Polar Components (γ P ) has.

[0035] In one embodiment, component (B) has a melting point of less than 166°C.

[0036] In one embodiment, component (B) has a glass transition temperature (Tg) of less than 25°C.

[0037] In one embodiment, component (B) has a surface tension of 0 mN / m or more and less than 1 mN / m. of Polar Components (γ P ) and may be a mixture of two or more non-polar polymers selected from the group consisting of polyethylene homopolymers, silane-functionalized polyethylene homopolymers, ethylene / alpha-olefin copolymers, and silane-functionalized ethylene / alpha-olefin copolymers.

[0038] In one embodiment, component (B) is present in an amount from 0 volume%, or from greater than 0 volume%, or from 30 volume% or more, or from 35 volume% or more, or from 40 volume% or more, to 50 volume% or less, or 49 volume% or less, or 48 volume% or less, or 45 volume% or less, or 42 volume% or less, based on the total volume of the composite.

[0039] Component C In one embodiment, the ternary polymer composite has (C) a surface tension of greater than 5 mN / m, or 6 mN / m or more, or 7 mN / m or more, or 8 mN / m or more. of Polar Components (γ P ) The copolymer comprises at least one copolymer of ethylene and an unsaturated ester ("component (C)") having the formula:

[0040] In one embodiment, copolymers of ethylene and unsaturated esters useful in the present disclosure contain from 5% by weight or more, or 10% by weight or more, or 15% by weight or more, or 20% by weight or more, to 50% by weight or less, or 40% by weight or less, or 35% by weight or less, or 30% by weight or less of one or more unsaturated esters, based on the total weight of the copolymer.

[0041] In one embodiment, unsaturated esters useful in the present disclosure include, but are not limited to, vinyl acetate, ethyl acrylate, and butyl acrylate. Preferably, the unsaturated ester is vinyl acetate.

[0042] In one embodiment, the melting point of component (C) is less than 166°C.

[0043] In one embodiment, the glass transition temperature (Tg) is less than 25°C.

[0044] In one embodiment, component (C) is crosslinked.

[0045] In one embodiment, component (C) has a surface tension of more than 5 mN / m, or 6 mN / m or more, or 7 mN / m or more, or 8 mN / m or more. of Polar Components (γ P ) The copolymer may be a mixture of two or more copolymers of ethylene and an unsaturated ester having the formula:

[0046] In one embodiment, component (C), the copolymer of ethylene and an unsaturated ester, is present in an amount of from 0 volume percent, or from greater than 0 volume percent, or from 30 volume percent or more, or from 35 volume percent or more, or from 40 volume percent or more, to 50 volume percent or less, or 49 volume percent or less, or 48 volume percent or less, or 45 volume percent or less, or 42 volume percent or less, based on the total volume of the composite.

[0047] Component D In one embodiment, the terpolymer composite comprises (D) at least one ethylene propylene diene monomer (EPDM) copolymer. Preferably, the at least one EPDM copolymer is an EPDM terpolymer ("Component (D)").

[0048] In one embodiment, the EPDM copolymer contains units derived from ethylene, units derived from propylene, and at least one conjugated or non-conjugated diene.

[0049] Exemplary conjugated dienes useful in the EPDM copolymers of the present disclosure include, for example, butadiene, isoprene, 2,3-dimethylbutadiene-1,3, 1,2-dimethylbutadiene-1,3, 1,4-dimethylbutadiene-1,3, 1-ethylbutadiene-1,3, 2-phenylbutadiene-1,3, heterdiene-1,3, 4-methylpentadiene-1,3, 1,3-pentadiene (CH 3 CH=CH-CH=CH 2 ;commonly called piperylene), 3-methyl-1,3-pentadiene, 2,4 dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene. Preferred conjugated dienes include butadiene and isoprene.

[0050] Exemplary non-conjugated dienes useful in the EPDM copolymers of the present disclosure include, for example, aliphatic dienes such as 1,4-pentadiene, 1,4-herediene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,6-heptadiene, 6-methyl-1,5-heptadiene, 1,6-octadiene, 1,7-octaden, 7-methyl-1,6-octadiene, 1,13-tetradecadiene, 1,19-eicosadiene; cyclic dienes such as 1,4-cyclohexadiene, bicyclo[2.2.1]hepta-2,5-diene, 5-ethylidene-2-noboronene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, bicyclic[2.2.2]octa-2,5-diene, These include 4-vinylcyclohex-1-ene, bicyclo[2.2.2]octa-2,6-diene, 1,7,7-trimethylbicyclo[2.2.1]hepta-2,5-diene, dicyclopentadiene, methyltetrahydroindene, 5-allylbicyclo[2.2.1]hept-2-ene, and 1,5-cyclooctadiene; aromatic dienes such as 1,4-diallylbenzene and 4-allyl-1H-indene; and trienes such as 2,3-diisopropenylidiene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, and 1,4,9-decatriene. Preferred non-conjugated dienes include dicyclopentadiene (DCPD), ethylidene norbornene (ENB), and vinyl norbornene (VNB).

[0051] Preferably, the diene is a non-conjugated diene. Preferably, the diene is a non-conjugated diene selected from the group consisting of DCPD, ENB, and VNB.

[0052] Typically, the EPDM copolymers contain, based on the total weight of the EPDM copolymer, 30% by weight or more, or 40% by weight or more, or 50% by weight or more, to 80% by weight or less, or 70% by weight or less, or 60% by weight or less, of units derived from ethylene; 15% by weight or more, or 20% by weight or more, or 25% by weight or more, to 60% by weight or less, or 55% by weight or less, or 50% by weight or less, of units derived from propylene; and greater than 0% by weight, or 0.1% by weight or more, or 0.5% by weight or more, to 10% by weight or less, or 5% by weight or less, or 2% by weight or less, of units derived from one or more dienes, e.g., conjugated or non-conjugated dienes.

[0053] In a preferred embodiment, the EPDM copolymer has a surface tension of greater than 5 mN / m, or 5.1 mN / m or greater, or 5.2 mN / m or greater, or 5.3 mN / m or greater. of Polar Components (γ P ) has.

[0054] In one embodiment, the melting temperature of component (D) is less than 166°C.

[0055] In one embodiment, the glass transition temperature (Tg) of component (D) is less than 25°C.

[0056] In one embodiment, component (D) is crosslinked.

[0057] In one embodiment, component (D) may be a mixture of two or more ethylene propylene diene monomer (EPDM) copolymers.

[0058] In one embodiment, component (D), i.e., the EPDM copolymer, is present in an amount of from 0 volume%, or from greater than 0 volume%, or from 30 volume% or more, or from 35 volume% or more, or from 40 volume% or more, to 50 volume% or less, or 49 volume% or less, or 48 volume% or less, or 45 volume% or less, or 42 volume% or less, based on the total volume of the composite.

[0059] Conductive Filler In one embodiment, the conductive filler is dispersed in only one of the components of the three-phase polymer composite, i.e., only one of components (A), (B), (C) and (D). Preferably, the conductive filler is dispersed in component (A).

[0060] In one embodiment, the conductive filler is selectively dispersed in only one component of the three-phase polymer composite, i.e., in one embodiment, the conductive filler is purposefully premixed with only one component of the three-phase polymer composite such that it is dispersed in only that one component in the final composition.

[0061] In one embodiment, the components (A), (B), (C) and (D) in which the conductive filler is not dispersed are essentially free of conductive filler. For example, when the conductive filler is dispersed in the component (A), the remaining two components selected from the components (B), (C) and (D) are essentially free of conductive filler. As used herein, "essentially free of conductive filler" means that the components other than the component containing the conductive filler contain 0.5% by volume or less, or 0.25% by volume or less, or 0.1% by volume or less, or 0.05% by volume or less of the conductive filler, respectively, based on the total volume of the component.

[0062] The conductive filler may be conventional carbon black, which is commonly used in semiconductor shielding.Other conductive fillers useful in the present disclosure include carbon fullerenes (preferably carbon nanotubes), graphite, graphene, other metal particles, and conductive polymers, such as polyacetylene, polyparaphenylene, polypyrrole, polythiophene, and polyaniline.Preferably, the conductive filler is selected from the group consisting of carbon black, carbon nanotubes, graphite, graphene, and combinations thereof.Most preferably, the conductive filler is carbon black.

[0063] Exemplary carbon blacks useful in this disclosure may have an average particle size of greater than 0 to 100 nanometers (nm), preferably 50 nm or less. In one embodiment, the carbon blacks useful in this disclosure have an average particle size of 700 nm or less. 2 / g or more to 1250m 2 / g or less, or 700m 2 / g or more to 900m 2 In one embodiment, the carbon black useful in this disclosure has an oil absorption (dibutyl phthalate or DBP) of from 200 ml / 100 g to 600 ml / 100 g or less, or from 300 ml / 100 g to 500 ml / 100 g or less.

[0064] In one embodiment, the particle size is about 35 nm or less, about 750 to 850 nm. 2 A suitable carbon black for use in the present disclosure is AKZO Ketjenblack EC300J, having a surface area (BET) of about 1.0 μm / g and an oil absorption of about 300-400 ml / 100 g.

[0065] In one embodiment, the conductive filler is present in the ternary polymer composite in an amount from greater than 0 vol.%, or 0.25 vol.% or more, or 0.5 vol.% or more, or 1 vol.% or more, or 1.5 vol.% or more, or 2 vol.% or more, or 3 vol.% or more, or 5 vol.% or more, or 10 vol.% or more to 30 vol.% or less, or 20 vol.% or less, or 15 vol.% or less, or 12 vol.% or less, based on the total volume of the composite.

[0066] composition The present disclosure provides a method for producing a polar component having a surface tension of 1 mN / m or more and 5 mN / m or less. (γ P ) (B) at least one copolymer of ethylene and an unsaturated ester having a surface tension of from 0.0 mN / m to less than 1 mN / m; of Polar Components (γ P )and (C) at least one non-polar polymer selected from the group consisting of polyethylene homopolymer, silane-functionalized polyethylene homopolymer, ethylene / alpha-olefin copolymer, and silane-functionalized ethylene / alpha-olefin copolymer; and (D) a surface tension of greater than 5 mN / m. of Polar Components (γ P ) and (D) at least two additional polymers selected from the group consisting of at least one copolymer of ethylene and an unsaturated ester having a structure represented by the formula:

[0067] In one embodiment, the composition comprises a three-phase polymer composite comprising components (A), (B) and (C), or components (A), (B) and (D), or components (A), (C) and (D). In one embodiment, the three-phase polymer composite comprises a conductive filler dispersed in component (A).

[0068] In one embodiment, the composition comprises a three-phase polymer composite comprising components (A), (B) and (C), wherein the conductive filler is dispersed in component (A).

[0069] In one embodiment, the composition comprises a three-phase polymer composite including components (A), (B) and (C), with the conductive filler dispersed in component (B).

[0070] In one embodiment, the composition comprises a three-phase polymer composite including components (A), (B) and (C), with the conductive filler dispersed in component (C).

[0071] In one embodiment, the composition comprises a three-phase polymer composite including components (A), (B) and (D), with the conductive filler dispersed in component (A).

[0072] In one embodiment, the composition comprises a three-phase polymer composite comprising components (A), (B) and (D), with the conductive filler dispersed in component (B).

[0073] In one embodiment, the composition comprises a three-phase polymer composite including components (A), (B) and (D), with the conductive filler dispersed in component (D).

[0074] In one embodiment, the composition comprises a three-phase polymer composite comprising components (A), (C) and (D), wherein the conductive filler is dispersed in component (A).

[0075] In one embodiment, the composition comprises a three-phase polymer composite including components (A), (C) and (D), with the conductive filler dispersed in component (C).

[0076] In one embodiment, the composition comprises a three-phase polymer composite including components (A), (C) and (D), with the conductive filler dispersed in component (D).

[0077] In one embodiment, the composition comprises components (A), (B) and (C), where component (B) is a polyethylene homopolymer or a silane-grafted polyethylene homopolymer. In one embodiment, the composition comprises components (A), (B) and (D), where component (B) is a polyethylene homopolymer or a silane-functionalized polyethylene homopolymer.

[0078] In one embodiment, the present disclosure provides a composition comprising: (A) a surface tension agent having a surface tension of 1 mN / m or more and 5 mN / m or less; of power Polar Components (γ P ) (B) at least one copolymer of ethylene and an unsaturated ester having a surface tension of from 0.0 mN / m to less than 1 mN / m; of Polar Components (γ P ) and (C) at least one non-polar polymer selected from the group consisting of polyethylene homopolymer, silane-functionalized polyethylene homopolymer, ethylene / alpha-olefin copolymer, and silane-functionalized ethylene / alpha-olefin copolymer; and (D) a surface tension of greater than 5 mN / m. of Polar Components (γ P ) and (D) at least two additional polymers selected from the group consisting of at least one copolymer of ethylene and an unsaturated ester having a molar ratio of 1:1 or 2:1; and (C) at least one ethylene propylene diene monomer copolymer; and a conductive filler dispersed in only one of the at least two additional polymers, wherein (i) a first polymer of the at least two additional polymers is selected from (B) and a second polymer of the at least two additional polymers is selected from (C) or (D), or (ii) a first polymer of the at least two additional polymers is selected from (C) and a second polymer of the at least two additional polymers is selected from (B) or (D), and the three-phase polymer composite is a multiphase composite, i.e., a composition in which each of the three polymer components is present as its own phase.

[0079] In one embodiment, the composition includes one or more additives. Such additives can be added to the composition before, during and / or after processing. The amount of additives is usually within the range of about 0.01% to about 3% by weight based on the total weight of the composition. Useful additives include additional antioxidants, crosslinking agents including organic peroxides, cure accelerators, coagents, scorch inhibitors and silanes.

[0080] In one embodiment, the composition has a conductivity, defined as the logarithm of volume resistivity (ohm-cm) versus percent conductive filler (volume %), of less than 9, or less than 7, or less than 5, or less than 4, or less than 3.

[0081] In one embodiment, the composition does not exhibit brittle fracture at room temperature.

[0082] In one embodiment, the composition comprises at least one crosslinking component, i.e., at least one of component (B), component (C) and component (D) is present in the composition and is crosslinked.

[0083] Methods of forming the composition In an embodiment, the present disclosure provides a coating composition comprising the following components: (A) a surface tension (γ P (B) at least one copolymer of ethylene and an unsaturated ester having a polar component of 0.0 mN / m or more and less than 1 mN / m in surface tension (γ P ), and selected from the group consisting of polyethylene homopolymers, silane-functionalized polyethylene homopolymers, ethylene / alpha-olefin copolymers, and silane-functionalized ethylene / alpha-olefin copolymers; (C) at least one non-polar polymer having a surface tension (γ P and (D) at least two additional polymers selected from the group consisting of: at least one copolymer of ethylene and an unsaturated ester having a polar component of at least one of the ethylene propylene diene monomer copolymers; and (A) at least two additional polymers selected from the group consisting of: at least one copolymer of ethylene and an unsaturated ester having a polar component of at least one of the ethylene propylene diene monomer copolymers; and a conductive filler dispersed in only one of the component (A) and the at least two additional polymers, wherein (i) a first polymer of the at least two additional polymers is selected from (B) and a second polymer of the at least two additional polymers is selected from (C) or (D), or (ii) a first polymer of the at least two additional polymers is selected from (C) and a second polymer of the at least two additional polymers is selected from (B) or (D).

[0084] In one embodiment, component (A) and at least two additional polymers are melt blended together with a conductive filler. In particular, in one embodiment, the method includes melt blending (A) to a surface tension (γ P (B) at least one copolymer of ethylene and an unsaturated ester having a polar component of 0.0 mN / m or more and less than 1 mN / m in surface tension (γ P ), and selected from the group consisting of polyethylene homopolymers, silane-functionalized polyethylene homopolymers, ethylene / alpha-olefin copolymers, and silane-functionalized ethylene / alpha-olefin copolymers; (C) at least one non-polar polymer having a surface tension (γ P (C) at least one copolymer of ethylene and an unsaturated ester having a polar component of at least one of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59,

[0085] Preferably, the conductive filler is melt blended with one of (A), (B), (C) and (D) to form a masterbatch. The masterbatch is then melt blended with the remaining two components of (A), (B), (C) and (D). In one embodiment, the conductive filler is melt blended with (A) to form a masterbatch. The masterbatch is then melt blended with (i) (B) and one of (C) or (D), or (ii) (C) and one of (B) or (D).

[0086] In one embodiment, the conductive filler is present in the masterbatch in an amount from 10% by weight or more, or 15% by weight or more, or 20% by weight or more, or 25% by weight or more, or 30% by weight or more, to 50% by weight or less, or 40% by weight or less, or 35% by weight or less.

[0087] Optionally, additional additives may be added before, during or after melt blending.

[0088] cable The present disclosure also provides cables, such as power cables, that include a layer (eg, a semiconducting layer) that includes the composite composition described herein.

[0089] In one embodiment, the present disclosure provides a cable, such as a power cable, comprising a conductor and a semiconducting layer covering at least a portion of the conductor, the semiconducting layer comprising the composite composition described herein. Preferably, the cable comprises a conductor, an inner semiconducting layer covering at least a portion of the conductor, an insulating layer covering at least a portion of the inner semiconducting layer, and an outer semiconducting layer covering at least a portion of the insulating layer, at least one of the inner and outer semiconducting layers comprising the composite composition described herein.

[0090] In embodiments, the inner and / or outer semiconducting layer has the following components: (A) a surface tension (γ P (B) at least one copolymer of ethylene and an unsaturated ester having a polar component of 0.0 mN / m or more and less than 1 mN / m in surface tension (γ P ), and selected from the group consisting of polyethylene homopolymers, silane-functionalized polyethylene homopolymers, ethylene / alpha-olefin copolymers, and silane-functionalized ethylene / alpha-olefin copolymers; (C) at least one non-polar polymer having a surface tension (γ P(A) at least one copolymer of ethylene and an unsaturated ester having a polar component of at least one of the at least two additional polymers; and (B) at least one ethylene propylene diene monomer copolymer; and (C) at least one additional polymer selected from the group consisting of: (A) at least one copolymer of ethylene and an unsaturated ester having a polar component of at least one of the at least two additional polymers; and (D) at least one additional polymer selected from the group consisting of: (A) at least one copolymer of ethylene and an unsaturated ester having a polar component of at least one of the at least two additional polymers; and (C) at least one additional polymer selected from the group consisting of: (A) at least one copolymer of ethylene and an unsaturated ester having a polar component of at least one of the at least two additional polymers; and

[0091] In one embodiment, the present disclosure provides a method of conducting electricity comprising applying a voltage through a cable disclosed herein.

[0092] definition Unless otherwise stated, all test methods are current as of the filing date of this disclosure.

[0093] As used herein, the term "composition" includes compositions and mixtures of materials, including reaction products and decomposition products formed from the materials of the composition.

[0094] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers, whether of the same or different kinds. Thus, the general term polymer includes the term homopolymer (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure), and the term copolymer, as defined herein below. For example, trace amounts of impurities, such as catalyst residues, may be incorporated into and / or within the polymer. As used herein, the term "copolymer" refers to a polymer prepared by polymerization of at least two different types of monomers. Thus, the general term copolymer includes bipolymers (used to refer to a polymer prepared from two different types of monomers), and polymers prepared from three or more different types of monomers.

[0095] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are specifically disclosed. To avoid ambiguity, all compositions claimed using the term "comprising" may include any additional additives, adjuvants, or compounds, whether or not polymeric compounds, unless otherwise stated. In contrast, the term "consisting essentially of" excludes from the scope of any succeeding description any other component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically recited. The term "or" refers to the recited members individually and in any combination, unless otherwise stated. The use of the singular includes the use of the plural, and vice versa.

[0096] Test Method Low resistance (<108 Ohm (Ω) Measurements: Low resistance measurements are performed using a Keithley 2700 Integra series digital multimeter with a 20-point probe. At least two specimens (101.6 mm length x 50.8 mm width x 1.9 mm thickness) are tested for each formulation. Electrical resistivity of the polymer composites is obtained from compression molded specimens. Silver paint (conductive silver #4817N) is applied to minimize contact resistance between the specimen and the electrodes.

[0097] High resistance (>10 8 Ω) Measurements: High resistance measurements are made using a disc sample of 76.2 mm diameter and 1.9 mm thickness using a Keithley Model 6517B electrometer high resistance meter and a Model 8009 resistivity test chamber.

[0098] Volume resistivity: Brittleness: The brittleness of a composite is tested by bending a rectangular specimen, 25.4 mm wide and 203.2 mm long, under load until the edges touch.

[0099] experiment The polymers, compositions, and methods of the present disclosure, and their uses, are more fully described by the following examples, which are provided for the purpose of illustrating the present invention and should not be construed as limiting the scope of the present invention.

[0100] material PP: Polypropylene homopolymer (MFR at 230°C (I 2.16 )=1.8g / 10min; density=0.935g / cc) PMMA: Poly(methyl methacrylate) (MFR at 230°C (I 2.16 )=12.1g / 10min; density=1.180g / cc) EAA-CB: Ethyl acrylate / carbon black masterbatch EAA: Ethyl acrylic acid (MFR at 230°C (I 2.16 )=8.5g / 10min; density=0.938g / cc) Si-LDPE: Ethylene-vinyltrimethoxysilane copolymer (MFR at 230°C (I 2.16 )=1.5g / 10min; density=0.920g / cc) EPDM: Ethylene propylene diene monomer rubber; a semi-crystalline hydrocarbon rubber with a diene level of 0.9% by weight based on the weight of the EPDM (Mooney viscosity at 125°C = 18) LDPE: Low density polyethylene (MFR at 230°C (I 2.16 )=2.3g / 10min; density=0.920g / cc) EVA: Ethylene-vinyl acetate (MFR at 230°C (I 2.16 )=3.0g / 10min; density=0.956g / cc) EEA: Ethylene-Ethyl Acrylate (MFR at 230°C (I 2.16 )=20g / 10min; density=0.930g / cc) EEA-CB: Ethylene- Ethyl Acrylate / Carbon Black Masterbatch The surface energy data for the above listed polymers is shown in Table 1 below.

[0101] [Table 1]

[0102] Comparative Examples 1-6 are prepared having the formulations shown in Table 2 below. Comparative PP / PMMA / (EAA-CB) composites are prepared similar to known prior art methods and are used to demonstrate the brittleness of the prior art systems. Conductive carbon black (CB) is premixed within the EAA polymer phase to form an EAA-CB masterbatch with a CB content of 9.3 volume percent based on the total volume of the masterbatch. The masterbatch is prepared by melt mixing using a 250 cc internal CW Brabender batch premixer. The EAA polymer and CB are charged directly into the mixing bowl of the batch premixer and compounded at 130°C for 10 minutes at 60 rpm. The EAA-CB masterbatch is combined with the other two polymers in the batch premixer and mixed at 190°C for 5 minutes at 60 rpm. The samples are then removed. The composites are then compression molded into 8 inch x 8 inch x 0.075 inch plaques. The polymer composites are compression molded at 135°C and 3.45 MPa for 5 minutes. After 5 minutes, the pressure is increased to 17 MPa, followed by a thermal anneal for 30 minutes at 190° C. The sample is then cooled to 30° C. and removed from the press.

[0103] Using a method similar to that used to make Comparative Examples 1-6, Comparative Examples 7-10 are prepared having the formulations shown in Table 1 below. An EAA-CB masterbatch is prepared as described for Comparative Examples 1-6 and then mixed with EEA to prepare a single-phase composite. The EAA-CB masterbatch and EEA are melt mixed at 40 rpm for 5 minutes at 135°C. A sample is then removed. The composite is compression molded into an 8" x 8" x 0.075" plaque. The polymer composite is compression molded at 135°C and 3.45 MPa for 5 minutes. After 5 minutes, the pressure is increased to 17 MPa, followed by a thermal anneal at 135°C for 15 minutes. The sample is then cooled to 30°C and removed from the press.

[0104] Inventive Examples 1-16 are prepared having the formulations shown in Table 1 below. In the inventive examples, conductive carbon black is premixed with the EEA polymer phase to form an EEA-CB masterbatch with a CB content of 20% by volume based on the total volume of the masterbatch. The masterbatch is prepared by melt mixing using a 250 cc internal CW Brabender batch premixer. The EEA and CB are charged directly into the mixing bowl of the batch premixer and compounded at 60 rpm for 10 minutes at 130°C. The masterbatch is combined with the other two polymers in the batch premixer and mixed at 40 rpm for 5 minutes at 135°C. The sample is then removed. The composite is then compression molded into an 8 inch x 8 inch x 0.075 inch plaque. The polymer composite is compression molded at 135°C and 3.45 MPa for 5 minutes. After 5 minutes, the pressure is increased to 17 MPa followed by a thermal anneal at 135°C for 15 minutes. The sample is then cooled to 30°C and removed from the press.

[0105] [Table 2]

[0106] The results for the composites (comparative and inventive examples) are shown in Table 3. Unlike comparative examples 1-6 (PP+PMMA+EAA-CB masterbatch), the inventive examples showed a reduced permeation threshold and achieved electrical conductivity at lower CB loadings. The reduced permeation threshold is particularly visible in FIG. 1. The inventive examples and comparative examples 7-10 are observed for failure and cracking when placed under load. The results show that the inventive examples are an improvement over the prior art single polymer systems. In particular, the inventive examples are an improvement over such prior art systems in terms of polymer systems with lower melting and glass transition temperatures, resulting in a more stable, more ductile / flexible system compared to that of the PP / PMMA system, which has a melting point and glass transition temperature that exceed the process limits and results in a very brittle material that is not suitable for many applications.

[0107]

Table 3

Claims

1. (A) at least one copolymer of ethylene and an unsaturated ester having a polar component of surface tension (γP) of 1 milliNewton per meter (mN / m) or more and 5 mN / m or less; (B) at least one non-polar polymer having a polar component of surface tension (γP) of 0 mN / m or more and less than 1 mN / m; (C) at least one copolymer of ethylene and an unsaturated ester having a polar component of surface tension (γP) of greater than 5 mN / m; and (D) at least two additional polymers selected from the group consisting of at least one ethylene propylene diene monomer copolymer; A conductive filler dispersed only in component (A), comprising a three-phase polymer composite comprising: The three-phase polymer composite comprises: a) component (A) is selected from the group consisting of ethylene-ethyl acrylate, ethylene-methyl acrylate, ethylene-butyl acrylate, and combinations thereof; Component (B) is selected from the group consisting of polyethylene homopolymer and silane-functionalized polyethylene homopolymer, and Component (C) is an ethylene-vinyl acetate having a polar component of surface tension (γP) of greater than 5 mN / m; Components (A), (B) and (C), or b) component (A) is selected from the group consisting of ethylene-ethyl acrylate, ethylene-methyl acrylate, ethylene-butyl acrylate, and combinations thereof; Component (D) is an EPDM terpolymer; Components (A), (C) and (D), or c) component (A) is selected from the group consisting of ethylene-ethyl acrylate, ethylene-methyl acrylate, ethylene-butyl acrylate, and combinations thereof; component (B) is selected from the group consisting of polyethylene homopolymer and silane-functionalized polyethylene homopolymer; Component (D) is an EPDM terpolymer; A composition comprising components (A), (B) and (D).

2. 10. The composition of claim 1, wherein the conductive filler is selected from the group consisting of carbon black, carbon nanotubes, graphite, graphene, and combinations thereof.

3. 3. The composition of claim 1 or 2, wherein component (B) is present and is selected from the group consisting of polyethylene homopolymer and silane-functionalized polyethylene homopolymer.

4. Component (A) is present in an amount of from greater than 0 volume percent to less than or equal to 40 volume percent, based on the total volume of the composite; a) component (B) is present in an amount of from greater than 0 volume % to less than or equal to 50 volume %, based on the total volume of the composite; b) component (C) is present in an amount of greater than 0 volume percent to less than or equal to 50 volume percent, based on the total volume of the composite; or The composition of any one of claims 1 to 3, wherein c) component (D) is present in an amount of from greater than 0 volume % to 50 volume % or less, based on the total volume of the composite.

5. A cable comprising a semiconducting layer comprising the composition according to any one of claims 1 to 4.

6. A conductor; an inner semiconductor layer covering at least a portion of the conductor; an insulating layer covering at least a portion of the inner semiconductor layer; an outer semiconducting layer covering at least a portion of the insulating layer, At least one of the inner and outer semiconductor layers is (A) at least one copolymer of ethylene and an unsaturated ester having a polar component of surface tension (γP) of 1 milliNewton per meter (mN / m) or more and 5 mN / m or less; (B) at least one non-polar polymer having a polar component of surface tension (γP) of 0 mN / m or more and less than 1 mN / m; (C) at least one copolymer of ethylene and an unsaturated ester having a polar component of surface tension (γP) of greater than 5 mN / m; and (D) at least two additional polymers selected from the group consisting of at least one ethylene propylene diene monomer copolymer; and and a conductive filler dispersed only in component (A), The three-phase polymer composite comprises: a) component (A) is selected from the group consisting of ethylene-ethyl acrylate, ethylene-methyl acrylate, ethylene-butyl acrylate, and combinations thereof; Component (B) is selected from the group consisting of polyethylene homopolymer and silane-functionalized polyethylene homopolymer, and Component (C) is an ethylene-vinyl acetate having a polar component of surface tension (γP) of greater than 5 mN / m; Components (A), (B) and (C), or b) component (A) is selected from the group consisting of ethylene-ethyl acrylate, ethylene-methyl acrylate, ethylene-butyl acrylate, and combinations thereof, and component (D) is an EPDM terpolymer; Components (A), (C) and (D), or c) component (A) is selected from the group consisting of ethylene-ethyl acrylate, ethylene-methyl acrylate, ethylene-butyl acrylate, and combinations thereof; component (B) is selected from the group consisting of polyethylene homopolymer and silane-functionalized polyethylene homopolymer; Component (D) is an EPDM terpolymer; Comprising components (A), (B) and (D), ,cable.

7. A method of electrical conduction comprising applying a voltage through the cable of claim 5 or 6.

8. 5. The composition of claim 1, wherein each of the at least two additional polymers comprises no more than 0.05 volume percent conductive filler, based on the total volume of each of the additional polymers.

9. The composition of claim 1 , wherein the composition does not exhibit brittle fracture at room temperature.

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