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    • 专利摘要:
    RETICULABLE POLYMER COMPOSITION, PROCESS TO PRODUCE A COATED CONDUCTOR AND CABLE. Crosslinkable polymeric compositions comprising an ethylene-based polymer, an organic peroxide and a polyallyl crosslinking coagent, wherein the polyallyl crosslinking coagent and the organic peroxide are present in sufficient amounts to provide an allyl-active oxygen molar ratio of at least 1 .6, based on the allyl content of the polyallyl crosslinking coagent and the active oxygen content of the organic peroxide. Such crosslinkable polymeric compositions can be employed in forming coated conductors.
    公开号:BR112015004914B1
    申请号:R112015004914-1
    申请日:2013-09-11
    公开日:2021-05-18
    发明作者:Jeffrey M. Cogen；Yabin Sun；Timothy J. Person；Lu Zhu
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    technical field
    [001] Several embodiments of the present invention relate to crosslinkable polymeric compositions. Other aspects of the invention relate to cross-linked polymeric compositions based on ethylene. Introduction
    [002] Medium, high and extra high voltage cables (“MV”, “HV” and “EHV”) typically contain a polymeric material based on ethylene crosslinked with peroxide as an insulating layer. Although crosslinking offers a valuable improvement in the thermomechanical properties of the material, the peroxide used in crosslinking creates by-products that require removal of the material after it is formed into an insulating layer (eg by degassing), however, before a jacketing layer is placed over the insulating layer. In the case of dicumyl peroxide, these by-products include methane, acetophenone, alpha methylstyrene, and cumil alcohol. To reduce the amount of by-products, the use of crosslinking co-agents has been investigated, and they can be employed to reduce the amount of peroxide used in crosslinking. Although advances in such coagents have been obtained, improvements are still desired. Invention Summary
    [003] One embodiment is a crosslinkable polymeric composition comprising: - an ethylene-based polymer; - an organic peroxide; and - a polyallyl crosslinking coagent, wherein said polyallyl crosslinking coagent and said organic peroxide are present in sufficient amounts to provide an allyl to active oxygen molar ratio of at least 1.6, based on the allyl content of said crosslinking coagent of polyallyl and the active oxygen content of said organic peroxide.
    [004] Another embodiment is a process for producing a coated conductor, said process comprising:
    [005] (a) coating a conductor with a crosslinkable polymeric composition, said crosslinkable polymeric composition comprising an ethylene-based polymer, an organic peroxide, and a polyallyl crosslinking coagent; and
    [006] (b) cure or allow to cure at least a portion of said crosslinkable polymeric composition, thereby forming a crosslinked polymeric coating,
    [007] wherein said polyallyl crosslinking coagent and said organic peroxide are present in said crosslinkable polymeric composition in sufficient amounts to provide an allyl to active oxygen molar ratio of at least 1.6, based on the allyl content of said coagent polyallyl crosslinker and the active oxygen content of said organic peroxide. Brief Description of Drawings
    [008] Reference is made to the attached drawings, where:
    [009] Figure 1 is a graph of MH-ML @ 180°C versus tsl' @ 140°C used to determine the relationship between scorch time and screen density for the peroxide crosslinked polymer . Detailed Description
    [010] Several embodiments of the present invention relate to crosslinkable polymeric compositions comprising an ethylene-based polymer, an organic peroxide and a polyallyl crosslinking coagent. Additional embodiments refer to crosslinked polymeric compositions prepared from crosslinkable polymeric compositions. Other embodiments relate to processes for producing a coated conductor using crosslinkable polymeric compositions. Crosslinkable Polymeric Composition
    [011] As noted above, one of the components of the polymeric compositions described herein is an ethylene-based polymer. As used herein, "ethylene-based" polymers are polymers prepared with ethylene monomers as the primary monomer component (i.e., greater than 50 percent by weight ("% by weight)), although other comonomers may also be employed. "Polymer" means a macromolecular compound prepared by reacting (i.e., polymerizing) monomers of the same or different type, and includes homopolymers and interpolymers. "Interpolymer" means a polymer prepared by polymerizing at least two different types of monomer. This generic term includes copolymers (generally used to refer to polymers made with two different types of monomer) and polymers made with more than two different types of monomer (eg, terpolymers (three different types of monomer) and tetrapolymers (four different types of monomer) monomer)).
    [012] In various embodiments, the ethylene-based polymer can be an ethylene homopolymer. As used herein, "homopolymer" denotes a polymer comprising repeating units derived from a simple type of monomer, although it does not exclude residual amounts of other components used in preparing the homopolymer, such as chain transfer agents.
    [013] In one embodiment, the ethylene-based polymer may be an ethylene/alpha-olefin ("α-olefin") interpolymer having an α-olefin content of at least 1% by weight, at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, or at least 25% by weight, based on the total weight of the interpolymer. Such interpolymers can have an α-olefin content of less than 50% by weight, less than 45% by weight, less than 40% by weight, or less than 35% by weight, based on the weight of the interpolymer. When an α-olefin is employed, the α-olefin can be a C3-20 α-olefin (ie, having 3 to 20 carbon atoms) linear, branched, or cyclic. Examples of C3-20 α-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene . α-olefins can also have a cyclic structure, such as cyclohexane or cyclopentane, resulting in an α-olefin, such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane. Ethylene/α-olefin interpolymers include ethylene/propylene, ethylene/butene, ethylene/1-hexene, ethylene/1-octene, ethylene/styrene, ethylene/propylene/1-octene, ethylene/propylene/butene, ethylene/butene/ 1-octene, and ethylene/butene/styrene.
    [014] In various embodiments, the ethylene-based polymer can be used alone or in combination with one or more types of ethylene-based polymers (eg, a mixture of two or more ethylene-based polymers that differ from each other by composition and monomer content, catalytic method of preparation, etc). If an ethylene-based polymer blend is employed, the polymers can be blended via any in-reactor or post-reactor process.
    [015] In various embodiments, the ethylene-based polymer may be selected from the group consisting of low density polyethylene ("LDPE"), linear low density polyethylene ("LLDPE"), very low density polyethylene ("VLDPE" ) and combinations of two or more of them.
    [016] In one embodiment, the ethylene-based polymer can be an LDPE. LDPEs are generally highly branched ethylene homopolymers, and can be prepared via high pressure processes (ie, HP-LDPE). LDPEs suitable for use in the present invention may have a density ranging from 0.91 to 0.94. In various embodiments, the ethylene-based polymer is a high pressure LDPE having a density of at least 0.915 g/cm3 but less than 0.94 or less than 0.93 g/cm3. The polymer densities provided herein are determined in accordance with the American Society for Testing and Materials (“ASTM”), method D792. LDPEs suitable for use in the present invention may have a melt index (I2) of less than 20g/10 min or ranging from 0.1 to 10g/10 min, from 0.5 to 5g/10 min, from 1 to 3g/10 min, or an I2 of 2g/10 min. Melting indices provided herein are determined in accordance with ASTM method D1238. Unless otherwise stated, melt indices are determined at 190°C and 2.16 kg (a.k.a., I2). Generally, LDPEs have a broad molecular weight distribution ("MWD") resulting in a high polydispersity index ("PDI;" ratio of weight average molecular weight to number average molecular weight).
    [017] In one embodiment, the ethylene-based polymer can be an LLDPE. LLDPEs are generally ethylene-based polymers, having a heterogeneous distribution of comonomer (eg, α-olefin monomer), and are characterized by short-chain branching. For example, LLDPEs can be copolymers of ethylene and α-olefin monomers, such as those described above. LLDPEs suitable for use in the present invention may have a density ranging from 0.916 to 0.925 g/cm3. LLDPEs suitable for use in the present invention may have a melt index (I2) ranging from 1 to 20g/10min, or from 3 to 8g/10min.
    [018] In one embodiment, the ethylene-based polymer can be a VLDPE. VLDPEs may also be known in the prior art as ultra-low density polyethylene, or ULDPEs. VLDPEs are generally ethylene-based polymers having a heterogeneous comonomer distribution (eg, α-olefin monomer) and are characterized by short chain branching. For example, VLDPEs can be copolymers of ethylene and α-olefin monomers, such as one or more of the α-olefin monomers described above. VLDPEs suitable for use in the present invention can have a density ranging from 0.87 to 0.915 g/cm3. VLDPEs suitable for use in the present invention may have a melt index (I2) ranging from 0.1 to 20g/10min, or from 0.3 to 5g/10min.
    [019] In one embodiment, the ethylene-based polymer may comprise a combination of any two or more of the ethylene-based polymers described above.
    [020] The production processes used to prepare ethylene-based polymers are wide, varied and known in the state of the art. Any conventional or later discovered production process to produce ethylene-based polymers having the above-described properties can be employed in preparing the ethylene-based polymers described herein. In general, the polymerization can be carried out under conditions known in the state of the art for polymerization reactions of the Ziegler-Natta or Kaminsky-Sinn type, that is, at temperatures ranging from 0 to 250°C, or from 30 or 200°C , and pressures ranging from atmospheric to 10,000 atmospheres (1,013 megaPascal (“MPa”)). In most polymerization reactions, the molar ratio of catalyst to polymerizable compounds employed is 10-12:1 to 10-1:1 or 10-9:1 to 10-5:1.
    [021] As noted above, the ethylene-based polymer described above is combined with an organic peroxide. As used herein, "organic peroxide" denotes a peroxide having the structure: R1-O-O-R2, or R1-O-O-R-O-O-R2, where each of R1 and R2 is a hydrocarbyl moiety, and R is a hydrocarbyl moiety. As used herein, the term "hydrocarbyl" denotes a univalent group formed by removing a hydrogen atom from a hydrocarbon (eg, ethyl, phenyl). As used herein, the term "hydrocarbylene" denotes a divalent group formed by removing two hydrogen atoms from a hydrocarbon. The organic peroxide can be any dialkyl, diaryl, dialkaryl, or diaralkyl peroxide, having the same or different alkyl, aryl, alkaryl, or aralkyl portions. In one embodiment, each of R1 and R2 is independently a C1 to C20 or C1 to C12 alkyl, aryl, alkaryl or aralkyl moiety. In one embodiment, R may be a C1 to C20 or C1 to C12 alkylene, arylene, alkarylene or aralkylene moiety. In various embodiments, R, R1 and R2 can have the same or different number of carbon atoms, or any two of R, R1 and R2 can have the same number of carbon atoms, while the third has a different number of carbon atoms.
    [022] Organic peroxides suitable for use in the present invention include monofunctional peroxides and difunctional peroxides. As used herein, "monofunctional peroxides" denote peroxides having a single pair of covalently bonded oxygen atoms (eg, having an R-O-O-R structure). As used herein, "difunctional peroxides" denote peroxides having two pairs of covalently bonded oxygen atoms (eg, having an R-O-O-R-O-O-R structure). In one embodiment, the organic peroxide is a monofunctional peroxide.
    [023] Representative organic peroxides include dicumyl peroxide ("DCP"); tert-butyl peroxybenzoate; di-teramyl peroxide ("DTAP"); bis-(t-butyl-peroxy isopropyl)benzene ("BIPB"); t-butyl isopropylcumyl peroxide; t-butylcumylperoxide; di-t-butyl peroxide; 2,5-bis(t-butylperoxy)-2,5-dimethylhexane; 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane; isopropylcumyl cumylperoxide; 4,4-di(tert-butylperoxy)butyl valerate; di(isopropylcumyl)peroxide; and mixtures of two or more of them. In various embodiments, only a simple type of organic peroxide is employed. In one embodiment, the organic peroxide is dicumyl peroxide.
    [024] As noted above, the crosslinkable polymer composition further includes a polyallyl crosslinking coagent. As used herein, the term "polyallyl" denotes a compound having at least two pendant allyl functional groups. In various embodiments, the crosslinking coagent is a triallyl compound. In certain embodiments, the crosslinking coagent is selected from the group consisting of triallyl isocyanurate ("TAIC"), triallyl cyanurate ("TAC"), triallyl trimellitate ("TATM") and mixtures of two or more thereof. In one embodiment, the crosslinking coagent is TAIC.
    [025] In various embodiments, the polyallyl crosslinking coagent constitutes all or substantially all of the crosslinking coagents present in the crosslinkable polymeric composition. In some embodiments, the crosslinkable polymeric composition is free or substantially free of nitroxide compounds (eg, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, or "TEMPO"). As used herein, "substantially free" denotes a concentration of less than 10 parts per million by weight based on the total weight of the crosslinkable polymer composition. In one or more embodiments, the crosslinkable polymeric composition is free or substantially free of vinyl-functional esters. In various embodiments, the crosslinkable polymeric composition is free or substantially free of acrylate compounds. In one or more embodiments, the crosslinkable polymeric composition is free or substantially free of di-vinyl styrene compounds. In various embodiments, the crosslinkable polymer composition is free or substantially free of alkadiene, alkatriene and/or alcatetraene compounds.
    [026] In various embodiments, the crosslinkable polymer composition may comprise the ethylene-based polymer in an amount ranging from 50 to 98.9% by weight, from 80 to 98.9% by weight, from 90 to 98.9% by weight, or from 95 to 98.9% by weight, based on the total weight of the crosslinkable polymer composition. In certain embodiments, the ethylene-based polymer is present at a concentration ranging from 95.6 to 99.6% by weight, or from 97.5 to 98.5% by weight, based on the combined weight of the base polymer. of ethylene, the organic peroxide, and the polyallyl crosslinking coagent. Additionally, the crosslinkable polymeric composition may comprise the organic peroxide in an amount ranging from 0.1 to 1.4% by weight, from 0.4 to 1.4% by weight, from 0.4 to 1.2% by weight , from 0.5 to 1.0% by weight, or from 0.7 to less than 1.0% by weight, based on the combined weight of the ethylene-based polymer, organic peroxide, and polyallyl crosslinking coagent . In one embodiment, the organic peroxide is present in the crosslinkable polymer composition in an amount of less than 1.4% by weight, or less than 1.0% by weight, based on the combined weight of the ethylene-based polymer, of the organic peroxide. , and the polyallyl crosslinking coagent. Furthermore, the crosslinkable polymeric composition may comprise the polyallyl crosslinking coagent in an amount ranging from 0.5 to 3% by weight, from 0.7 to 3% by weight, from 1.0 to 3% by weight, or from 1.5 to 3% by weight, based on the combined weight of the ethylene-based polymer, the organic peroxide, and the polyallyl crosslinking coagent. In one embodiment, the polyallyl crosslinking coagent is present in the crosslinkable polymeric composition in an amount of at least 0.5% by weight, at least 0.85% by weight, or at least 1% by weight, based on weight. combined ethylene-based polymer, organic peroxide and polyallyl crosslinking coagent.
    [027] In various embodiments, the polyallyl crosslinking coagent and the organic peroxide are present in a weight ratio of at least 1.0, at least 1.2, at least 1.5, or at least 2.0, and up to 10.0, crosslinking coagent/organic peroxide.
    [028] In various embodiments, the polyallyl crosslinking coagent and the organic peroxide are present in sufficient amounts to obtain a molar ratio of allyl groups to active oxygen groups of at least 1.6, at least 1.9, at least 2, 5, or at least 3.0, and up to 5, up to 7.5, up to 10, up to 12, or up to 16 allyl groups/active oxygen atoms. In determining this relationship, only oxygen atoms present as one of two covalently bonded oxygen atoms in the organic peroxide are considered “active oxygen atoms”. For example, a monofunctional peroxide has two active oxygen atoms. Oxygen atoms present in the organic peroxide or polyallyl crosslinking coagent that are not covalently bonded to another oxygen atom are not considered active oxygen atoms. Additionally, only pendant allyl groups found in the polyallyl crosslinking coagent are included in the allyl groups/active oxygen atoms molar ratio. The molar ratio of allyl to active oxygen is calculated as follows: (moles of polyallyl coagent)(number of allyl groups per molecule of coagent/(moles of peroxide)(number of active oxygen atoms per molecule of peroxide)
    [029] The crosslinkable polymeric composition may also contain other additives, including, but not restricted to processing aids, fillers, coupling agents, ultraviolet absorbers or stabilizers, antistatic agents, nucleating agents, slip agents, plasticizers, lubricants, control agents viscosity agents, tackifiers, antiblocking agents, surfactants, thinner oils, acid scavengers, flame retardants, and metal deactivators. Additives, other than fillers, are typically used in amounts ranging from 0.01 or less than 10 or more percent by weight, based on the total weight of the composition. Fillers are generally added in larger amounts, although the amount can range from as low as 0.01 or less to 65 or more % by weight, based on the total weight of the composition. Illustrative examples of fillers include clays, precipitated silica and silicates, fumed silica, calcium carbonate, ground minerals, aluminum trihydroxide, magnesium hydroxide, and carbon blacks with typical arithmetic mean particle sizes greater than 15 nanometers.
    [030] Additionally, an antioxidant can be employed with the crosslinkable polymeric composition. Representative antioxidants include hindered phenols (eg, tetracis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane); phosphites and phosphonites (eg tris(2,4-di-t-butylphenyl)phosphate); thio compounds (ex: dilaurylthiodipropionate); various siloxanes; and various amines (eg, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline). Antioxidants can be used in amounts of 0.1 to 5% by weight based on the total weight of the crosslinkable polymer composition. In forming wire and cable compositions, discussed below, antioxidants are typically added to the system prior to processing (i.e., prior to extrusion and cross-linking) of the finished article.
    [031] In various embodiments, the crosslinkable polymeric composition may be free or substantially free of anti-scorching agents. For example, the crosslinkable polymeric composition can be free or substantially free of α-tocopherol.
    [032] In various embodiments, the crosslinkable polymer composition may be free or substantially free of polyalkylene glycols. In various embodiments, the crosslinkable polymeric composition can be free or substantially free of elastomeric polymers. In various embodiments, the crosslinkable polymer composition can be free or substantially free of carboxylic acid/ester-modified polymers (e.g., ethylene/ethyl acrylate copolymers).
    [033] The preparation of the crosslinkable polymeric composition may comprise the formulation of the above-described components. For example, formulation can be conducted by (1) formulating all components in the ethylene-based polymer, or (2) formulating all components except the organic peroxide, which is immersed as described below. The formulation of the crosslinkable polymeric composition can be carried out using standard equipment known to those skilled in the art. Examples of formulation equipment are internal batch mixers, such as the BrabenderTM, BanburyTM or BollingTM internal mixer. Alternatively, single-screw or twin screw continuous mixers can be used, such as the Farrel™ continuous mixer, a Werner and Pfleiderer™ twin screw mixer, or a Buss™ continuous extruder. The formulation can be conducted at a temperature greater than the melting temperature of the ethylene-based polymer to a temperature above which the ethylene-based polymer begins to degrade. In various embodiments, the formulation can be conducted at a temperature ranging from 100 to 200°C, or from 110 to 150°C. In various embodiments, the immersion of the organic peroxide into the ethylene-based polymer can be conducted at a temperature ranging from 30 to 100°C, from 50 to 90°C, or from 60 to 80°C.
    [034] Alternatively, in one or more embodiments, the organic peroxide and the polyallyl crosslinking coagent can be immersed in the ethylene-based polymer, either simultaneously or sequentially. In one embodiment, the organic peroxide and polyallyl crosslinking coagent may be premixed at a temperature above the melting temperature of the organic peroxide and polyallyl crosslinking coagent, whichever is greater, followed by dipping of the ethylene-based polymer. in the resulting mixture of organic peroxide and polyallyl crosslinking coagent at a temperature ranging from 30 to 100°C, from 50 to 90°C or from 60 to 80°C, for a period of time ranging from 1 to 168 hours, 1 to 24 hours, or 3 to 12 hours. In another embodiment, the ethylene-based thermoplastic polymer can be immersed in the organic peroxide at a temperature ranging from 30 to 100°C, from 50 to 90°C, or from 60 to 80°C, for a period of time ranging from 1 to 168 hours, 1 to 24 hours or 3 to 12 hours, followed by immersion of the ethylene-based polymer in polyallyl crosslinking coagent at a temperature ranging from 30 to 100°C, from 50 to 90°C, or from 60 to 80°C, for a period of time ranging from 1 to 168 hours, from 1 to 24 hours, or from 3 to 12 hours. In yet another embodiment, the ethylene-based polymer can be immersed in the polyallyl crosslinking coagent at a temperature ranging from 30 to 100°C, from 50 to 90°C, or from 60 to 80°C, for a period of time. ranging from 1 to 168 hours, from 1 to 24 hours, or from 3 to 12 hours, followed by immersion of the ethylene-based polymer in organic peroxide at a temperature ranging from 30 to 100°C, from 50 to 90°C, or from 60 to 80°C, for a period of time ranging from 1 to 168 hours, from 1 to 24 hours, or from 3 to 12 hours. In yet another embodiment, the ethylene-based polymer can be immersed in organic peroxide and polyallyl crosslinking coagent without premix at a temperature ranging from 30 to 100°C, from 50 to 90°C, or from 60 to 80° C, for a time period ranging from 1 to 168 hours, 1 to 24 hours, or 3 to 12 hours. Crosslinked Polymeric Composition
    [035] The crosslinkable polymer composition described above can be cured or allowed to cure to form a crosslinked ethylene-based polymer. This cure can be conducted by subjecting the crosslinkable polymer composition to elevated temperatures in a heated cure zone, which can be maintained at a temperature in the range of 175 to 260°C. The heated cure zone can be heated using pressurized steam or inductively heated using pressurized nitrogen gas. The crosslinked polymer composition can then be cooled (eg to room temperature).
    [036] The crosslinking process can create volatile decomposition by-products in the crosslinked polymeric composition. The term “volatile decomposition products” denotes decomposition products formed during the curing step, and possibly during the cooling step, upon initiation of organic peroxide. These by-products can comprise alkanes such as methane. In various embodiments, the crosslinked polymeric composition initially comprises (i.e., prior to degassing, described below) methane in a maximum amount of 860 parts per million ("ppm") or less, 750 ppm or less, 700 ppm or less, or 650 ppm or less, 600 ppm or less, 550 ppm or less, 500 ppm or less, 450 ppm or less, or 400 ppm or less, based on the total weight of the crosslinked polymer composition.
    [037] After crosslinking, the crosslinked polymer composition can be subjected to degassing to remove at least a part of the volatile decomposition by-products. Degassing can be conducted at a degassing temperature, a degassing pressure, and a degassing period to produce a degassed polymeric composition. In various embodiments, the degassing temperature can range from 50 to 150°C, or from 60 to 80°C. In one embodiment, the degassing temperature is 65 to 75°C. Degassing can be conducted under standard atmosphere pressure (ie 101,325 Pa).
    [038] The degree of crosslinking in the crosslinked polymeric composition can be determined via analysis in a moving matrix rheometer (“MDR”) at 180°C, according to ASTM D 5289. In the analysis, an increase in torque, as indicated by difference between the maximum torque (“MH”) and the minimum torque (“ML”) (“MH-ML”), indicates a greater degree of crosslinking. The resulting crosslinked polymeric composition may have an MH-ML of at least 2.5 dN.m, at least 2.75 dN.m, at least 3 dN.m, at least 3.25 dN.m, at least 3. 5 dN.m or at least 3.75 dN.m, with a practical maximum limit of 6 dN.m. In one embodiment, the cross-linked polymeric composition may have an MH-ML ranging from 2.5 to 6 dN.m, from 2.75 to 6 dN.m, from 3 to 6 dN.m, from 3.25 to 6 dN .m, from 3.6 to 6 dN.m or from 3.75 to 6 dN.m.
    [039] In various embodiments, the crosslinked polymeric composition can have an improvement in scorching ("SI") of at least 10, at least 11, at least 12, at least 15, or at least 20, and up to 25, up to 30, up to 40, up to 50, up to 60, or up to 70. The improvement in scorching is determined according to the procedures described in the Test Methods section, below. Coated Conductor
    [040] A cable comprising a conductor and an insulating layer can be prepared using the crosslinkable polymer composition described above. “Cable” and “power cord” mean at least one wire or optical fiber inside a sheath, for example, an insulating jacket or a protective outer jacket. Typically, a cable comprises two or more strands or optical fibers joined together, typically in a common insulating jacket and/or protective jacket. The individual strands or fibers within the sheath can be bare (bare), coated or insulated. Combined cables can contain both electrical wires and optical fibers. Typical cable designs are illustrated in USP 5,246,783, 6,496,629, and 6,714,707. “Conductor” denotes one or more wire(s) or fiber(s) to conduct heat, light, and/or electricity. The conductor may be of the single-strand/single-fiber or multi-strand/multi-fiber type and may be filament or tubular in form. Non-limiting examples of suitable conductors include metals such as silver, gold, copper, carbon and aluminum. The conductor can also be an optical fiber made of glass or plastic.
    [041] This cable can be prepared with several types of extruders (eg, single-screw or double-screw types) by extruding the crosslinkable polymeric composition over the conductor, either directly or over the intervening layer. A description of a conventional extruder can be found in USP 4,857,600. An example of a co-extrusion and extruder can therefore be found in USP 5,575,965.
    [042] After extrusion, the extruded cable may be passed to a heated curing zone downstream of the extrusion die to aid in crosslinking the crosslinkable polymer composition and thereby producing a crosslinked polymer composition. The heated cure zone can be maintained at a temperature in the range of 175 to 260°C. In one embodiment, the heated cure zone is a continuous scorch tube (“CV”). In various embodiments, the crosslinked polymeric composition can then be cooled and degassed, as discussed above.
    [043] Alternating current cables, prepared in accordance with the present invention, can be low, medium, high or extra-high voltage. Furthermore, direct current cables in accordance with the present invention include high or extra-high voltage cables. Test Methods Sample Preparation for Examples 1-6
    [044] For Examples 1-6, feed polyethylene ("PE") pellets containing antioxidant (~0.36% by weight) to a Brabender mixer at 130°C with a rotor speed of 30 rpm and premix the crosslinking coagent as soon as the PE melts. Mixing time after addition of crosslinking coagent is 5 minutes. Heat the resulting compost in an oven at 90°C for 1 hour, then feed it into a two-roll laminator at 120°C. After the PE melts, the peroxide is added, followed by mixing at a roll speed of 12 rpm and roll distance of 0.6 mm for 4 minutes. The PE employed is DFDA-4850NT, from Dow Chemical Company, Midland, MI, USA, which has a density of 0.92 g/cm3 and a melt index (I2) of 2g/10 min. The antioxidant used is Cyanox 2212, already mixed in DFDA-4850, from Cytec Industries, Woodland Park, NJ, USA. The peroxide employed is dicumyl peroxide ("DCP" from Sigma-Aldrich, St. Louis, MO, USA Crosslinking coagents are described below. Compression Molding
    [045] Using a Lab Tech LP-S-50/ASTM laboratory hydraulic press, preheat the sample coated on both sides with two polyethylene terephthalate (“PET”) membranes in the mold at 130°C for 5 minutes. Release the air trapped in the sample by opening and closing the plate eight times. Increase plate temperature to 182°C for 8 minutes. Cure the sample under a pressure of 100 kN for 15 minutes. Reduce plate temperature to 45°C for 5 minutes. Moving Matrix Rheometer
    [046] Conduct the test in the moving matrix rheometer (“MDR”) at 180°C, according to the methods described in ASTM D5289 on an Alpha Technologies MDR 2000 using samples cut from the sheet prepared with the double cylinder laminator or saturated pellets. Mechanical Properties (Traction)
    [047] Determine mechanical properties in accordance with ASTM D638 on an Instron model 5565 tensile tester using cured and compression molded specimens. Electrical Properties
    [048] Determine the electrical constant and dissipation factor at 50 or 60 Hz, as specified below, and 1 kV per ASTM D150 on a 1 mm plate using cured and compression molded samples. Improved scorching
    [049] The improvement in scorching for an X sample prepared with either DCP or a polyallyl crosslinking coagent is calculated using the following formula: SI = ts1@140°C - ts1'@140°C where SI is the improvement of scorching, ts1@140°C is the scorching time of sample X measured by MDR at 140°C, and ts1'@140°C is the predicted scorching time of a theoretical sample having the same formulation as sample X, however without crosslinking coagent, the prediction is based on the crosslink density (MH-ML) of sample X. The predicted scorching time is calculated according to the following formula (1): ts1'@140°C = -7 .97 + (167.91/(MH-ML@180°C)) where MH-ML@180°C is the screen density of sample X measured via MDR at 180°C. Formula (1) is determined based on comparisons of eight samples prepared with polyethylene and dicumula peroxide alone (ie without crosslinking coagent) to determine the relationship between scorch time and crosslink density (MH-ML) for samples without crosslinking coagent. Samples are prepared as described above in the Sample Preparation section, according to the formulas in Table 1, and analyzed via MDR according to the above methods: Table 1: Scorching Improvement - Formula Determination Samples (1)

    [050] Plotting the data presented in Table 1 using MH-ML@180°C versus ts1@140°C yields formula (1). The JMPTM statistical analysis software is used to adjust the data in Table 1 and arrive at formula (1). The relationship between MH-ML and ts1@140°C is reciprocal (at least in the common DCP load range). Therefore, MH-ML is first transformed into its reciprocal form, 1/(MH-ML), and then to a line between ts1@140°C and 1/(MH-ML). This produces the equation (formula(1)) between ts1@140°C and MH-ML. The steps used to generate formula (1) in the JMPTM statistical analysis software are listed below: 1. Click analyze/adjust on X; 2. Select MH-ML in X, factor and ts1@140°C in Y, answer; 3. Click on the red upper left triangle, select “special setting”; 4. Select Reciprocal: 1/x in the transformation column X and click on the OK button.
    [051] The results of this analysis are given in Figure 1.
    [052] With respect to the Scorch Improvement values, a negative SI indicates a worsening in the anti-scorching property, whereas a positive SI indicates an improvement in that property, with higher positive SI values being preferred for superior end-use performance.
    [053] Methane Content (Multiple Headspace Extraction via Headspace Gas Chromatography)
    [054] Conduct Multiple Headspace Extraction ("MHE") using Headspace Gas Chromatography ("HSGC") under the following conditions: Instrumentation Gas Chromatography Agilent 6890 Injection port with divider/no divider DB-5MS column, 30m x 0, 32mm x 1.0mm FID Detector G1888 Sample Entry ChemStation Data Collection G1888 Headspace Conditions GC Cycle Time 60 minutes Oven Temperature 150ºC Loop Temperature 160ºC Transfer Line Temperature 170ºC Bottle Equilibrium Time 60 minutes Agitation Speed off Loop fill time 0.20 min Loop equilibrium time 0.05 min Injection time 0.50 min Pressurizing time 0.50 min Feed functions Multi HS Ext on; 5 extractions per bottle Conditions GC 6890 Carrier gas (EPC) nitrogen, 2.0 mL/min Inlet temperature 250ºC Divider ratio 1:10 Flow mode Constant flow Temperature FID 300ºC Oven program 40ºC, hold 3 min; ramp up to 280°C at a rate of 15°C/min; hold for 5 minutes (24 min total) Detector FID@300ºC Hydrogen 40 mL/min; air 450 ml/min; preparation (nitrogen) 45 mL/min
    [055] Equilibrate the sample at some temperature for a certain period of time and analyze the headspace (top) above the sample. Repeat this balancing and measurement process multiple times, an exponential reduction in peak areas being observed. Place ~1.0g samples into 22ml headspace vials and analyze according to the conditions given below. Eq.(1):
    An = peak area of the injection A1 = peak area of the first injection
    [056] According to Eq. (1), only two values are needed to calculate the total peak areas: A1 and constant K. The first is a measured value, while the last one can be obtained from regression analysis linear of the following equation: Eq. (2): 1n An = -K(n-1)+1n A1
    [057] Having the sum of the peak area values, it only needs a calibration factor that expresses the relationship between the peak area and the concentration (quantity) of the analyte. Standard methane calibration curve
    [058] Inject the following amounts of methane into HSGC vials, 200 μl, 400 μl, 500 μl, 600 μl, 800 μl, and 1000 μl. Build correlation between total peak area oo
    and methane content. Place two pieces of the compression molded sample (prepared as described above) with dimensions of 10mm x 50mm x 1mm in a HSGC bottle for the HSGC test in order to obtain the total peak area 00

    [059] Then prepare a standard calibration curve for area versus μl of methane, and use that standard calibration curve to calculate the methane content (μl/g) based on the total peak area
    for each sample. Then, the methane content unit was transformed from μl/g into ppm, by calculating the methane density. Density
    [060] Determine density according to ASTM D792. Fusion Index
    [061] Measure the melt index, or I2, according to ASTM D1238, condition 190°C/2.16 kg, and report in grams eluted for 10 minutes. Measure I10 according to ASTM D1238, condition 190°C/10 kg, and report in grams eluted for 10 minutes. Examples Example 1 - Polyethylene Crosslinking with High Triallyl Coagent:DCP Ratio
    [062] Prepare and cure five Comparative Samples (CS1-CS5) and nine Samples (S1-S9) according to the formulations shown in Table 2, below, using the procedures described in the Test Methods section above. Triallyl isocyanurate (“TAIC”) (99%) employed is supplied by Shanghai Fangruida Chemicals Co., Ltd. Triallyl cyanurate (“TAC”) (97%) employed is supplied by Fluka AG. The triallyl trimellitate (“TATM”) (96%) employed is supplied by Meryer (Shanghai) Chemical Technology Co., Ltd. The polyethylene and DCP employed are the same as those described in the Test Methods section above. Table 2 - Compositions of CS1-CS6 and S1-S9

    [063] Analyze all samples listed in Table 2 in accordance with the MDR and Scorching Improvement procedures described in the Test Methods section above. The results of these analyzes are shown in Table 3 below. Table 3 - MDR and SI Analysis of Cross-linked Polyethylene Samples

    [064] As shown in Table 3, compared to the Comparative Samples, S1-S9 show better performance, both with regard to healing and anti-scorching. For example, the ts1@140°C of S4 is almost 70 minutes, which suggests better anti-scorching performance.
    [065] The improvement in scorching (“SI”) is an indicator of the effects of crosslinking coagents on the scorching property. It is an effective way to compare the anti-scorching property of samples with the same screen density (MH-ML). As shown in Figure 3, as the coagent load increases, so does the SI. Furthermore, after the coagent:DCP weight ratio increases to at least 1 (allyl group to active oxygen molar ratio of at least 1.6), as in Samples S1 to S5, the SI is greater than that of Comparative Samples CS1 to CS4, which have a coagent:DCP weight ratio of less than 1.
    [066] Additionally, Samples S6 to S9 show that TATM and TAC also achieve an SI greater than 10, with a coagent to DCP weight ratio greater than 1. Example 2: High Coagent Ratio Crosslinked Polyethylene Methane Content of Triallyl:DCP
    [067] Prepare two additional Comparative Samples (CS6 and CS7), according to the formulations shown in Table 4, below, using the procedures described in the Test Methods section above. Comparative Sample CS8, DOW ENDURANCETM HFDB-4201 SC, is a cross-linkable, long-life, low-density polyethylene insulating compound from The Dow Chemical Company, Midland, MI, USA. Polyethylene and DCP are the same as described above in Example 1. Table 4 - Compositions of CS6-CS8

    [068] Determine the methane content and screen density (MH-ML) of Samples S1 and S2, and Comparative Samples CS1, CS2, and CS6-CS8 in accordance with the procedures given in the Test Methods section above. The results are shown in Table 5 below. Table 5 - Methane Content

    [069] As noted in Table 5, when reducing the DCP load, the methane content of S1 and S2 is lower than all Comparative Samples, with the exception of CS6 which has a DCP load of only 0.7 % by weight. CS6, however, has an unacceptably low lattice density of 0.99 dN.m. Example 3 - Mechanical Properties of Crosslinked Polyethylene with High Triallyl Coagent:DCP Ratio
    [070] Determine the mechanical properties (ie, tensile strength and tensile elongation) of Samples S1-S4 and Comparative Samples CS1-CS5, according to the procedures presented in the Test Methods section. The results are shown in Table 6, below. Table 6 - Mechanical Properties

    [071] The results presented above show that the mechanical properties of Samples S1-S4 are maintained even with an increase in the ratio of coagent to DCP. Example 4 - Electrical Properties of Crosslinked Polyethylene with High Triallyl Coagent:DCP Ratio
    [072] Determine the electrical properties (ie, dielectric constant and dissipation factor) of Samples S1 and S4 and Comparative Samples CS1 and CS3, according to the procedures presented in the Test Methods section. The results are shown in Table 7, below. Table 7 - Electrical Properties

    [073] Determine the dissipation factor at high temperature (100°C), high voltage (20 kV/mm) and 60 Hz for Samples S2 and S3 and Comparative Sample CS8. The results are shown in Table 8, below. Table 8 - Mechanical Properties

    [074] As shown in Tables 7 and 8, although the addition of coagent caused a small increase in the dissipation factor, both at room temperature and at high temperature/high voltage, the Samples still meet the specifications and fall within current practice industrial. Example 5 - Polyethylene Crosslinking with Wide Triallyl Coagent Ratio Range: DCP
    [075] Prepare six additional Samples (S10-S15) and one additional Comparative Sample (CS9) in accordance with the formulations shown in Table 9, below, using the procedures described in the Test Methods section above. The polyethylene employed in these samples is the same as described in Examples 1-6 above (i.e., DFDA-4850 NT, from Dow Chemical Company, Midland, MI, USA). The DCP and TAIC are also the same as those described above in Example 1. Table 9

    [076] Analyze all samples listed in Table 9, in accordance with the MDR and Scorching Improvement procedures described in the Test Methods section above. The results of these analyzes are given in Table 10, below. Table 10 - MDR and SI Analysis of Cross-linked Polyethylene Samples

    [077] The results presented in Table 10 indicate that extremely high molar ratios of active allyl-oxygen (eg ~50, as in CS9) may be unfeasible. However, active allyl-oxygen molar ratios as high as 7.5 to 12.2 (as in S10 and S11) provide excellent scorch improvement while maintaining screen density. Additionally, increasing the DCP content while maintaining the active allyl-oxygen molar ratio tends to cause reductions in the scorching improvement, as shown by comparing S13 with S15. Example 6 - Crosslinking of Polyethylene with Acrylate-Based Coagents
    [078] Prepare seven additional Comparative Samples (CS10-CS16), according to the formulations shown in Table 11, below, using the procedures described in the Test Methods section above. Table 11 - Sample Compositions with Acrylate-Based Coagents

    [079] Analyze all samples listed in Table 11, according to the MDR procedure described in the Test Methods section above. The results of these analyzes are shown in Table 12 below. Comparative Sample 1 and Sample 2 are shown again in Table 12 for comparison purposes. Table 12 - MDR Analysis of Samples Cross-linked with Acrylate-Based Coagents

    [080] The results presented in Table 12 indicate that acrylate-based coagents do not provide sufficient screening density, as evidenced by the low values of MH-ML. Example 7 - Immersion of Coagent and DCVP in Polyethylene Formulation Procedure for Comparative Samples
    [081] Feed polyethylene pellets containing antioxidants into a Brabender mixer at 130°C with a rotor speed of 30 rpm. After the polyethylene is melted, add the coagent. Mixing time after addition of coagent is 5 minutes. Then feed this compound into a two-roll laminator at 120°C after pre-heating the sample in an oven at 90°C. After the polyethylene compound has melted, add the peroxide dropwise, then mix at a roll speed of 12 rpm and roll distance of 0.6 mm for 4 minutes. Pre-Mixing Procedure for Samples
    [082] Place DCP crystals in a vial, inject TAIC liquid with syringe into the vial and place it in an oven at 60°C for about 10 minutes. Remove the vial and shake until obtaining a homogeneous liquid mixture of the initial biphasic liquid. Sample Immersion Procedure
    [083] Place polyethylene pellets in a vial, inject liquid DCP, TAIC or the pre-mixed mixture of TAIC and DCP in the vial, seal the vial and shake it manually for about 1 minute to ensure liquid distribution over all the pellets. Then place the bottle in an oven at 80°C for 9 hours. Sample Preparation
    [084] Using the procedures described, prepare two Comparative Samples (CS17 and CS18) and three Samples (S16-S18) using the formulations in Table 13, below. S16 and S17 are prepared by immersing the polyethylene pellets in the mixture of TAIC and DCP. S18 is prepared by sequentially soaking the polyethylene in DCP at 80°C for 9 hours, followed by soaking in TAIC at 85°C for 9 hours. In each of these samples, the polyethylene, DCP and TAIC used are the same as those described above in Example 1. Table 13 - Compositions of CS17, CS18 and S16-S18

    [085] Analyze all samples listed in Table 13 in accordance with the MDR and SI procedures listed in the Test Methods section above. The results of these analyzes are shown in Table 14 below. Table 14 - MDR and SI analysis of CS18, CS19 and S16-S18

    [086] Observing the results provided in Table 14, above, there is a comparable increase in MH and scorching time when employing the immersion procedure described above compared to the formulation procedure. Specifically, CS17 and S16 have the same composition, although S16 exhibited a higher MH and comparable scorching time. Similarly, CS18, S17, and S18 have the same composition, although S17 and S18 exhibit a higher MH and comparable scorch time. Example 8 - Peroxide Variation
    [087] Prepare nine additional Samples (S19-S27) according to the formulations provided in Table 15, below, and using the same procedure described above for preparing Samples S1-S6, except for the use of different peroxides. In the example below, BIPB is bis(t-butyl-peroxy-isopropyl)benzene, supplied by Shanghai Fangruida Chemical Co., Ltd. LUPROXTM 101 is 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, provided by Arkema. DTAP is di-ter-amyl peroxide, from Arkema. Polyethylene, DCP and TAIC are the same as described above for Samples S1-S6. Table 15 - Compositions of S19-S27

    [088] Analyze all samples listed in Table 15 in accordance with the MDR procedures cited in the Test Methods section above. The results of these analyzes are given in Table 16, below. Table 16 - MDR Analysis of S19-S27 Crosslinked Polyethylene Samples

    [089] As can be seen, based on the results presented in Table 16, varying the type of peroxide away from DCP, while at the same time employing an allyl-active oxygen ratio of at least 1.6, still provides a cross-linked polyethylene with adequate screen density.
    权利要求:
    Claims (10)
    [0001]
    1. Crosslinkable polymeric composition, characterized in that it comprises: - an ethylene-based polymer, said ethylene-based polymer being an ethylene homopolymer; - an organic peroxide; and - a polyallyl crosslinking coagent, wherein said polyallyl crosslinking coagent and said organic peroxide are present in sufficient amounts to provide an allyl/active oxygen molar ratio of 7.5 to 16, based on the allyl content of said crosslinking coagent of polyallyl and the active oxygen content of said organic peroxide, the crosslinkable polymer composition further comprising an antioxidant which is a hindered phenol or a thio compound.
    [0002]
    2. Composition according to claim 1, characterized in that said organic peroxide is present in said crosslinkable polymeric composition in an amount of less than 1.4 percent by weight, based on the combined weight of said ethylene-based polymer said organic peroxide and said polyallyl crosslinking coagent; wherein said polyallyl crosslinking coagent is present in said crosslinkable polymeric composition in an amount of at least 0.5 percent by weight, based on the combined weight of said ethylene-based polymer, said organic peroxide, and said crosslinking coagent of polyallyl; wherein said ethylene-based polymer is present in said crosslinkable polymeric composition in an amount ranging from 50 to 98.9 percent by weight, based on the total weight of the crosslinkable polymeric composition.
    [0003]
    3. Composition according to any one of claims 1 or 2, characterized in that said polyallyl crosslinking coagent is a triallyl compound; said organic peroxide being a monofunctional peroxide.
    [0004]
    4. Composition according to any one of claims 1 or 2, characterized in that said polyallyl crosslinking coagent is selected from the group consisting of triallyl isocyanurate ("TAIC"), triallyl cyanurate ("TAC"), trimethylate triallyl ("TATM") and mixtures of two or more thereof; said organic peroxide being dicumyl peroxide.
    [0005]
    5. Composition according to any one of claims 1 to 4, characterized in that said crosslinkable polymeric composition is substantially free of scorching inhibitors.
    [0006]
    6. Process for producing a coated conductor, characterized in that it comprises: (a) coating a conductor with a cross-linkable polymer composition, said cross-linkable polymer composition comprising an ethylene-based polymer, said ethylene-based polymer is a homopolymer of ethylene, an organic peroxide, and a polyallyl crosslinking coagent; and (b) curing or allowing to cure at least a portion of said crosslinkable polymeric composition, thereby forming a crosslinked polymeric coating, wherein said polyallyl crosslinking coagent and said organic peroxide are present in said crosslinkable polymeric composition in sufficient amounts to provide an allyl to active oxygen molar ratio of 7.5 to 16, based on the allyl content of said polyallyl crosslinking coagent and the active oxygen content of said organic peroxide, the crosslinkable polymer composition further comprising an antioxidant that is a hindered phenol or a thio compound.
    [0007]
    7. Process according to claim 6, characterized in that said organic peroxide is present in said crosslinkable polymeric composition in an amount of less than 1.4 percent by weight, based on the combined weight of said ethylene-based polymer , said organic peroxide, and said polyallyl crosslinking coagent; wherein said polyallyl crosslinking coagent is present in said crosslinkable polymeric composition in an amount of at least 0.5 percent by weight, based on the combined weight of said ethylene-based polymer, said organic peroxide, and said polyallyl crosslinking coagent ; wherein said ethylene-based polymer is present in said crosslinkable polymeric composition in an amount ranging from 50 to 98.9 percent by weight, based on the total weight of the crosslinkable polymeric composition.
    [0008]
    8. Process according to any one of claims 6 or 7, characterized in that said polyallyl crosslinking coagent is selected from the group consisting of triallyl isocyanurate ("TAIC"), triallyl cyanurate ("TAC"), trimethylate triallyl ("TATM") and mixtures of two or more thereof; said organic peroxide being dicumyl peroxide.
    [0009]
    9. Process according to any one of claims 6 to 8, characterized in that said crosslinkable polymeric composition is substantially free of scorch inhibitors, said crosslinked polymeric coating having a crosslink density (MH-ML) of hair minus 2.5 dN.m.
    [0010]
    10. Cable, characterized in that it is prepared in accordance with the process to produce a coated conductor as defined in any one of claims 6 to 9.
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    同族专利:
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    WO2014040237A1|2014-03-20|
    EP2895540A4|2016-04-20|
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    JP2019007013A|2019-01-17|
    KR20200067935A|2020-06-12|
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    US20150203701A1|2015-07-23|
    MX363920B|2019-04-05|
    EP2895540A1|2015-07-22|
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    KR20150054808A|2015-05-20|
    EP2895540B1|2019-08-14|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-18| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CNPCT/CN2012/081275|2012-09-12|
    PCT/CN2012/081275|WO2014040237A1|2012-09-12|2012-09-12|Cross-linkable polymeric compositions, methods for making the same, and articles made therefrom|
    PCT/CN2013/083289|WO2014040532A1|2012-09-12|2013-09-11|Cross-linkable polymeric compositions, methods for making the same, and articles made therefrom|
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