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    • 专利摘要:
    Crosslinkable Mixture and Fusion Molded Article A crosslinkable mix is disclosed comprising: a polyolefin, an alkoxysilane, an organopolysiloxane, a free radical initiator and a liquid polymer modifier. The organopolysiloxane contains two or more hydroxyl end groups. When the melt molded crosslinkable mixture forms a single crosslinked composition. The liquid polymer modifier improves the flexibility of the melt molded article without decreasing dielectric strength.
    公开号:BR112012006019B1
    申请号:R112012006019-8
    申请日:2010-09-14
    公开日:2021-05-11
    发明作者:Mohamed Esseghir；Jeffrey M. Cogen；Saurav S. Sengupta
    申请人:Union Carbide Corporation；
    IPC主号:
    专利说明:

    field of invention
    [0001] This disclosure relates to crosslinked melt molded articles. In one aspect, the disclosure relates to a process for producing crosslinked melt molded articles, while in another aspect, the disclosure relates to such a process in which the articles are crosslinked using an organopolysiloxane containing two or more terminal functional groups. In another aspect, the invention relates to such a process in which crosslinking is carried out without requiring the use of moisture or external heat post-molding. Invention history
    [0002] Compositions used in the manufacture of crosslinkable articles, such as heat resistant wire and cable coatings and molded parts and fittings, typically require crosslinking after final molding. Various methods of crosslinking are practiced in the art, two of which are widely used, i.e., peroxide crosslinking and moisture curing (the latter of which usually employs a copolymerized or silane-grafted polyolefin).
    [0003] Moisture curing systems are advantageous in that they can be processed within a wide range of melting temperatures, but are generally limited to thin-walled structures because crosslinking relies on external moisture diffusion into the article. Peroxide curing compositions are preferred for thick walled structures, for example molded cable fittings and medium voltage (MV) cable insulation. These curable compounds need to be processed at temperatures that are below the peroxide decomposition temperature in order to avoid premature cross-linking (pre-vulcanization) before forming the article. Once the article is formed, it needs to be uniformly heated to the peroxide decomposition temperature, and then held for as long as necessary to achieve the desired level of crosslinking. This can keep the production rate for such articles low due to reduced heat transfer through the article walls. Furthermore, once the article has cooled the peroxide decomposition decreases to negligible levels; thus, any meaningful crosslinking comes to an end. The associated problems of pre-vulcanization and long heat-up and cure times (either in-mold cure time or residence time in a continuous vulcanizing tube) lead to long manufacturing cycles, and consequently low productivity (units per time).
    [0004] In crosslinked polyolefin articles, particularly in wire and cable applications, flexibility is desired. Flexibility in wire and cable coating promotes proper cable winder as well as handling during cable splicing. Flexibility in wire and cable accessories promotes ease of installation across a wide range of cable sizes.
    [0005] Oil extender additives are known to improve the flexibility of crosslinked articles. However, the addition of oil thinners to crosslinked articles has its drawbacks. In particular, the addition of oil diluent to the crosslinked articles results in a decrease in the dielectric strength (ACBD) of the crosslinked article.
    [0006] There is a need for flexible crosslinked polyolefin articles with high dielectric strength. There is still a need for flexible crosslinked polyolefin articles for wire and cable applications. Invention Summary
    [0007] The present disclosure relates to crosslinked polyolefin articles with improved flexibility and high dielectric strength. The present crosslinked articles include a crosslinked polyolefin and a liquid polymer modifier. The polyolefin is cross-linked via a single silane bond. Liquid polymer modifier improves flexibility without negatively affecting dielectric strength.
    [0008] The present disclosure provides a crosslinkable mixture that includes a polyolefin, an alkoxysilane, an organopolysiloxane, a free radical initiator and a liquid polymer modifier. The organopolysiloxane contains two or more hydroxyl end groups. In one embodiment, the crosslinkable mixture contains a crosslink catalyst.
    [0009] The present disclosure provides another crosslinkable blend that includes a silane grafted polyethylene, an organopolysiloxane and a liquid polymer modifier. The organopolysiloxane contains two or more hydroxyl end groups. In one embodiment, the crosslinkable mixture contains a crosslink catalyst.
    [0010] The present disclosure provides a melt-molded article that includes a cross-linked polyethylene composition, an organopolysiloxane, and a liquid polymer modifier. The organopolysiloxane contains two or more hydroxyl end groups.
    [0011] In one embodiment, the melt-molded article includes polysiloxane linkages between the polymeric polyethylene chains, the polysiloxane linkages having the structure (I):
    where n=1 to 100,000. Brief description of the drawings
    [0012] Figure 1 is a graph reporting dynamic mechanical analysis (DMA) data of an ENGAGE plastomer and an ENGAGE plastomer modified by reaction with hydroxyl-terminated polydimethylsiloxane (PDMS).
    [0013] Figure 2 is a schematic of a cross-section of a molded electrical connector comprising a thick-walled insulating layer sandwiched between two semiconductor layers.
    [0014] Figure 3 is a graph reporting DMA of an insulating layer of Figure 2.
    [0015] Figures 4A and 4B show electron micrographs of polyethylene grafted with VTMS mixed with hydroxy-terminated polydimethylsiloxane without catalyst and therefore non-crosslinked. Micrographs are at magnifications of 250X and 500X respectively.
    [0016] Figures 5A and 5B show electron micrographs of VTMS grafted polyethylene mixed with hydroxy terminated polydimethylsiloxane in the presence of a catalyst and crosslinked according to an embodiment of the present disclosure. Micrographs are at magnifications of 250X and 500X respectively. Detailed Description
    [0017] Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure. For purposes of US patent practice, the contents of any patent, parent application, or publication mentioned herein are hereby incorporated in their entirety by reference (or its equivalent US version also incorporated by reference) especially with respect to the disclosure of synthetic techniques, definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure), and general knowledge in the art.
    [0018] In this disclosure, the numerical ranges are approximate, and therefore may include values outside the range unless otherwise indicated. Numeric ranges include all their values including the lower and higher values, in increments of one unit, provided there is a separation of at least two units between any lower value and any higher value. As an example, if a compositional, physical or other property, such as, for example, molecular weight, viscosity, melt index, etc., is from 100 to 1000, it is intended that all individual values, such as 100 , 101, 102, etc., and subranges such as 100 to 144, 155 to 170, 197 to 200, etc., are expressly listed. For ranges containing values less than one or containing fractional numbers greater than one (eg 1.1, 1.5, etc.), a unit is considered, where appropriate, to be 0.0001, 0.001, 0.01 or 0.1. For ranges containing single digit (digit) numbers less than ten (eg 1 to 5), one unit is typically considered to be 0.1. These are only examples of what is specifically intended, and all possible combinations of numerical values enumerated between the minimum value and the maximum value will be considered as expressly stated in this disclosure. Within this disclosure, numerical ranges are provided for, among other things, amounts of composition components and various process parameters.
    [0019] “Ambient conditions” and similar terms mean the temperature, pressure and humidity of the environment or area surrounding an article. Ambient conditions in a typical laboratory or commercial building include a temperature of 23°C and atmospheric pressure.
    [0020] "Mixture", "polymer blend" and similar terms mean a blend of two or more polymers. Such a mixture may or may not be miscible. Such a mixture may or may not be separated into phases. Such a mixture may or may not contain one or more domain configurations, determined by transmission electron microscopy, light scattering, X-ray scattering, and any other method known in the art.
    [0021] “Cable” and similar terms mean at least one wire or optical fiber within an insulation, jacket or protective coating. Typically, a cable comprises two or more strands or optical fibers joined together, typically in a common insulation, jacket or protective sheath. The individual strands or fibers within the jacket can be bare, covered or insulated. Combination cables can contain both electrical wires and optical fibers. The cable, etc., can be designed for low, medium or high voltage applications. Typical cable designs are illustrated in ESP 5,246,783, 6,496,629 and 6,714,707.
    "Catalytic amount" means an amount of catalyst necessary to promote crosslinking of an ethylene/vinyl silane polymer at a detectable level, preferably at a commercially acceptable level.
    [0023] “Composition” and similar terms mean a mixture or combination of two or more components. For example, in the context of preparing a silane grafted ethylene polymer, a composition would include at least one ethylene polymer, at least one vinyl silane, and at least one free radical initiator. In the context of preparing a cable coating or other article of manufacture, a composition would include an ethylene/vinyl silane copolymer, a catalytic cure system and any desired additives such as lubricants, fillers, antioxidants and the like.
    [0024] "Reticulated", "cured" and similar terms mean that the polymer, before or after being molded into an article, has been subjected or exposed to a treatment that induced crosslinking and has extractables in xylene or dekalene less than or equal to 90 percent by weight (i.e., greater than or equal to 10 weight percent gel content). As used herein, a "cross-linkable blend" is a polymer blend that, when subjected to melt molding, forms a bond (i.e., a cross-link) between at least two individual polymer chains of the polymer.
    [0025] "Ethylene polymer", "polyethylene" and similar terms mean a polymer containing units derived from ethylene. Typically, ethylene polymers comprise at least 50 mole percent (mol%) of ethylene-derived units.
    [0026] "Ethylene/vinyl silane polymer" and similar terms mean an ethylene polymer comprising silane functionality. The silane functionality can be the result of polymerizing ethylene with a vinyl silane, for example, a vinyl trialkoxysilane comonomer, or grafting such comonomer onto an ethylene polymer backbone as described, for example, in USP 3,646,155 or 6,048. 935.
    [0027] "Interpolymer" and "copolymer" mean a polymer prepared by polymerizing at least two different types of monomers. These generic terms include both classical copolymers, ie polymers made from two different monomers, and polymers made from more than two different types of monomers, eg terpolymers, tetrapolymers, etc.
    [0028] "Fusion molded" and similar terms refer to an article manufactured from a thermoplastic composition that has acquired a configuration as a result of processing in a mold or through a die while in a molten state. The melt molded article may be partially crosslinked to maintain the integrity of its configuration. Fusion molded articles include wire and cable coatings, compression and injection molded parts, sheets, tapes, bands and the like.
    "Polymer" means a polymeric compound prepared by reacting (i.e., polymerizing) monomers either of the same type or of different types. Consequently, the generic term polymer encompasses the term "homopolymer", usually used to refer to polymers prepared from only one type of monomer, and the term "interpolymer" as defined above.
    [0030] "Propylene polymer", "polypropylene" and similar terms mean a propylene polymer containing units derived from propylene. Typically, propylene polymer comprises at least 50 mole percent (mole %) of units derived from propylene.
    [0031] The present disclosure provides a crosslinkable mixture. The crosslinkable mixture includes a polyolefin, an alkoxysilane, an organopolysiloxane, and a liquid polymer modifier. The organopolysiloxane contains two or more hydroxyl end groups. The crosslinkable mixture may optionally include a free radical initiator and/or a crosslinking catalyst.
    [0032] The polyolefin can be one or more C2-C12 polyolefins and combinations thereof. Non-limiting examples of suitable polyolefins include one or more propylene polymers, one or more ethylene polymers, and any combination thereof. Ethylene Polymers
    [0033] In an embodiment, the polyolefin is a polyethylene. Polyethylenes used in the practice of this disclosure to graft silane, i.e., polyethylenes that are subsequently grafted with a silane, can be produced using conventional polyethylene polymerization technology, e.g., high pressure catalysis, Ziegler-Natta, metallocene or geometry constricted. In one embodiment, polyethylene is prepared using a high pressure process. In another embodiment, polyethylene is prepared using transition metal catalysts (preferably Group 4) of mono- or bis-cyclopentadienyl, indenyl or fluorenyl or constrained geometry (CGC) catalysts in combination with an activator, in a solution process, semi-fluid slurry (slurry), or in gaseous phase. Preferably, the catalyst is a mono-cyclopentadienyl, mono-indenyl or mono-fluorenyl CGC. The solution process is preferred. USP 5,064,802, WO 93/19104 and WO 95/00526 disclose metal complexes of constrained geometry and methods for their preparation. Differently substituted indenyl containing metal complexes are taught in WO 95/14024 and WO 98/49212.
    [0034] In general, the polymerization can be carried out under conditions well known in the art for polymerization reactions of the Ziegler-Natta or Kaminsky-Sinn type, i.e., at temperatures of 0-250°C, preferably 30200°C, and pressures from atmospheric to 1013 megaPascal (MPa) (10,000 atmospheres). If desired, polymerization in suspension, solution, slurry (slurry), gas phase, solid state powder or other process conditions may be employed. The catalyst may or may not be supported on a support, and the composition of the support may vary widely. Representative supports are silica, alumina or a polymer (especially poly(tetrafluoroethylene or a polyolefin), and desirably a support is employed when using the catalyst in a gas phase polymerization process. the support is in an amount sufficient to provide a weight ratio of catalyst (based on metal) to support within a range of from 1:100,000 to 1:10, more preferably from 1:50,000 to 1:20, and most preferably from 1:10,000 to 1:30. In most polymerization reactions, the molar ratio of catalyst to polymerizable compounds employed is from 10-12:1 to 10-1:1, more preferably from 10-9:1 to 10-5 :1.
    [0035] Inert liquids serve as suitable solvents for polymerization. Examples include straight chain and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methyl-cyclohexane, methyl-cycloheptane, and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C4-10 alkanes; and alkyl substituted aromatic and aromatic compounds such as benzene, toluene, xylene, and ethylbenzene.
    [0036] Ethylene polymers useful in the practice of this invention include ethylene/α-olefin interpolymers having an α-olefin content of approximately 15, preferably of at least about 20 and even more preferably of at least about 25% in weight, based on the weight of the interpolymer. Typically, these interpolymers have an α-olefin content of less than about 50, preferably less than about 45, more preferably less than about 40 and even more preferably less than about 35% by weight, based on the weight of the interpolymer. . The α-olefin content is measured by 13 C nuclear magnetic resonance (NMR) spectroscopy using the procedure described in Randall (Rev. Macromol. Chem. Phys., C29 (2&3)). Generally, the higher the α-olefin content of the interpolymer, the lower the density and the more amorphous the interpolymer, and this translates into desirable physical and chemical properties for the protective insulating layer.
    [0037] Preferably, the α-olefin is a linear, branched or cyclic C320 α-olefin. 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. The α-olefins can also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3-cyclohexyl-1-propene (allyl-cyclohexane) and vinyl-cyclohexane. While not α-olefins in the classical sense of the term, for the purposes of this disclosure, certain cyclic olefins, such as norbornene and related olefins, particularly 5-ethylidene-2-norbornene, are α-olefins and may be used in place of some or all of the α-olefins described above. Similarly, styrene and its related olefins (eg, α-methyl-styrene, etc.) are α-olefins for the purposes of this invention. Illustrative ethylene polymers include copolymers of ethylene/propylene, ethylene/butene, ethylene/1-hexene, ethylene/1-octene, ethylene/styrene, and the like. Illustrative terpolymers include those of ethylene/propylene/1-octene, ethylene/propylene/butene, ethylene/butene/1-octene, ethylene/propylene/diene monomer (EPDM) and ethylene/butene/styrene. Copolymers can be random or block.
    [0038] The ethylene polymers used in the practice of this disclosure can be used alone or combined with one or more other ethylene polymers, for example, a mixture of two or more ethylene polymers "that differ from each other", which means that ethylene polymers are unusual by at least one property such as: by composition and content of monomer/comonomer, melting temperature, degree of branching, catalytic method of preparation, etc. If the ethylene polymer is a blend of two or more ethylene polymers, then the ethylene polymer may be blended by any reactor or post-reactor process. Mixing processes in reaction to post-reactor mixing processes are preferred, and processes using multiple reactors connected in series are preferred reactor mixing processes. These reactors can be loaded with the same catalyst, but operated under different conditions, for example, different concentrations of reactants, temperatures, pressures, etc., or operated under the same conditions, but loaded with different catalysts.
    [0039] Examples of ethylene polymers prepared with high pressure processes include (but are not limited to) low density polyethylene (LDPE), ethylene/silane reactor copolymer (such as SiLINK® produced by The Dow Chemical Company), ethylene/vinyl acetate (EVA) copolymer, ethylene/ethyl acrylate (EAA) copolymer, and ethylene/silane/acrylate terpolymers.
    [0040] Other examples of ethylene polymers that can be grafted with silane functionality include very low density polyethylene (VLDPE) (eg FLEXOMER® ethylene/1-hexene polyethylene produced by The Dow Chemical Company), ethylene/copolymers homogeneously branched linear α-olefin polymers (eg, TAFMER® produced by Mitsui Petrochemicals Company Limited and EXACT® produced by Exxon Chemical Company), homogeneously branched substantially linear ethylene/α-olefin polymers (eg, AFFINITY® and ENGAGE® polyethylenes obtainable from The Dow Chemical Company), and ethylene block copolymers (eg, INFUSE® polyethylene obtainable from The Dow Chemical Company). The most preferred ethylene polymers are substantially linear and linear homogeneously branched ethylene copolymers. Substantially linear ethylene copolymers are especially preferred, and are described more fully in USP 5,272,236, 5,278,272 and 5,986,028.
    [0041] In one embodiment, the crosslinkable blend includes a first polyethylene and a second polyethylene that is different from the first polyethylene. The first polyethylene has at least one unusual structure or property (not the same) as compared to the second polyethylene. Polyethylene is prepared which is copolymerized with silane functionality using a high pressure process.
    [0042] Silane functionality
    [0043] In the case where the polyolefin is grafted with silane, the crosslinkable mixture includes an alkoxysilane. In the practice of this disclosure, any alkoxysilane can be used which will effectively copolymerize with ethylene, or will graft and cross-link an ethylene polymer, and those described by the following formula are exemplary:
    in which R1 is a hydrogen atom or methyl group; x and y are 0 or 1 with the proviso that when x is 1, y is 1; men are independently an integer from 0 to 12 inclusive, preferably from 0 to 4, and each R" is independently a hydrolyzable organic group such as an alkoxy group having 1 to 12 carbon atoms (e.g., methoxy , ethoxy, butoxy), aryloxy group (eg phenoxy), araloxy group (eg benzyloxy), aliphatic acyloxy group having 1 to 12 carbon atoms (eg formyloxy, acetyloxy, propanoyloxy), amino or amino groups substituted (alkylamino, arylamino), or a lower alkyl group having from 1 to 6 carbon atoms inclusive, with the proviso that no more than one of the three R groups is an alkyl group. Such alkoxysilane can be copolymerized with ethylene in a reactor, such as a high pressure process. Such alkoxysilane can also be grafted to an appropriate ethylene polymer by using an appropriate amount of organic peroxide, before or during a shaping or molding operation. Additional ingredients such as light and heat stabilizers, pigments, pre-vulcanization retardants, etc. may also be included in the formulation. The phase of the process during which crosslinks (cross-links) are created is commonly referred to as the “cure phase” and the process itself is commonly referred to as the “cure”. Also included are alkoxysilane which is added on unsaturation to the polymer via free radical processes, such as mercaptopropyl trialkoxysilane.
    Suitable alkoxysilanes include unsaturated silanes comprising an ethylenically unsaturated hydrocarbyl group, such as a vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or gamma-(meth)acryloxyallyl group, and a hydrolyzable group, such as for example, a hydrocarbyloxy, hydrocarbonyloxy, or hydrocarbylamino group. Examples of hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, and alkyl or arylamino groups. Preferred alkoxysilanes are unsaturated alkoxysilanes which can be grafted onto the polymer or copolymerized in the reactor with other monomers (such as ethylene and acrylates). These alkoxysilanes and their method of preparation are more fully described in USP 5,266,627 to Meverden, et al. Vinyl trimethoxysilane (VTMS), vinyl triethoxysilane, vinyl triacetoxysilane, gamma-(meth)acryloxypropyl trimethoxysilane, and mixtures of these silanes are the preferred silane crosslinkers for use in this disclosure.
    [0045] In the practice of this disclosure, the amount of silane crosslinker used may vary widely depending on the nature of the polymer, alkoxysilane, processing or reactor conditions, grafting or copolymerization efficiency, end application, and factors similar, but typically at least 0.5, preferably at least 0.7 percent by weight is used. Convenience and economic considerations are two of the major limitations on the maximum amount of alkoxysilane crosslinker used in the practice of this disclosure, and typically the maximum amount of alkoxysilane crosslinker does not exceed 5, preferably does not exceed 3 percent by weight.
    [0046] The alkoxysilane crosslinker is grafted onto the polymer by any conventional method, typically in the presence of an initiator via free radicals, e.g. peroxides, or by ionizing radiation, etc. Organic initiators are preferred, as are any of the peroxide initiators, for example, dicumyl peroxide, di-tertiarybutyl peroxide, tertiarybutyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, tertiarybutyl peroctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(tertiarybutyl peroxy)hexane, and tertiarybutyl peracetate. The amount of initiator can vary, but typically it is present in an amount of at least 0.04, preferably at least 0.06 part per hundred parts of resin (% by weight). Typically, the initiator does not exceed 0.15, preferably does not exceed about 0.10% by weight. The weight ratio of silane crosslinker to initiator can also vary widely, but the typical weight ratio of crosslinker to initiator is from 10:1 to 500:1, preferably between 18:1 and 250:1. When used in parts per hundred parts of resin or phr, the term "resin" means the olefinic polymer.
    [0047] While any conventional method can be used to graft the alkoxysilane crosslinker onto the polyolefin polymer, a preferred method is to mix the two with the initiator in the first stage of a reactive mixing or extrusion process, such as a Buss kneader or a twin screw extruder. Grafting conditions may vary, but melting temperatures are typically between 160 and 260°C, preferably between 190 and 230°C, depending on the residence time and half-life of the initiator.
    [0048] The copolymerization of vinyl trialkoxysilane crosslinkers with ethylene and other monomers can be done in a high pressure reactor that is used in the preparation of homopolymers and copolymers with vinyl acetate and acrylates. Polyfunctional organopolysiloxane with end functional groups
    [0049] The crosslinkable mixture includes an organopolysiloxane, such as a polyfunctional organopolysiloxane having two or more functional end groups. Oligomers containing terminal functional groups useful in the present process comprise from 2 to 100,000 or more units of the formula R2SiO in which each R is independently selected from the group consisting of alkyl radicals comprising from 1 to 12 carbon atoms, alkenyl radicals comprising from 2 to about of 12 carbon atoms, aryl radicals, and fluorine-substituted alkyl radicals comprising from 1 to about 12 carbon atoms. The radical R can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl, dodecyl, vinyl, allyl, phenyl, naphthyl, tolyl, and 3,3,3-trifluoro-propyl. It is preferred when each R radical is methyl.
    In one embodiment, the organopolysiloxane contains one or more hydroxyl end groups such as a hydroxyl terminated polydimethylsiloxane containing at least two hydroxyl end groups. Such polydimethylsiloxanes are commercially obtainable, for example, as silanol terminated polydimethylsiloxane from Gelest, Inc. However, polydimethylsiloxanes having other end groups can be used which can react with grafted silanes, for example, polydimethylsiloxanes with amine end groups and the like. In preferred embodiments, the polydimethylsiloxane is of the formula:
    where Me is methyl and n is in the range of 1 to 100,000 or more. The value "n" can have a lower limit of 1, or 2, or 3, or 4, or 5, or 10, or 15, or 20 and an upper limit of 50, or 75, or 100, or 120, or 400, or 1000, or 100,000. Non-limiting examples of suitable polyfunctional organopolysiloxanes are: the silanol terminated polydimethylsiloxane DMS-15 (Mn 2000-3500, viscosity 45-85 centistoke, -OH level 0.9-1.2%) from Gelest Corp. , and Silanol Fluid 1-3563 (viscosity 55-90 centistoke, -OH level 1-1.7%) from Dow Corning Corp. In some embodiments, the polyfunctional organopolysiloxane comprises branches such as those imparted by Me-SiO3/2 or SiO4/2 groups (known as T or Q groups to those skilled in silicone chemistry).
    [0051] In the practice of this invention, the amount of polyfunctional organopolysiloxane used may vary widely depending on the nature of the polymer, alkoxysilane, polyfunctional organopolysiloxane, processing or reactor conditions, end application, and similar factors, but typically use at least 0.5, preferably at least 2 percent by weight. Convenience and economic considerations are two of the major limitations on the maximum amount of polyfunctional organopolysiloxane used in the practice of this disclosure, and typically the maximum amount of polyfunctional organopolysiloxane does not exceed 20, preferably does not exceed 10 percent by weight. Crosslinking Catalyst
    [0052] The crosslinkable mixture optionally includes a crosslinking catalyst. Crosslinking catalysts include Lewis and Bronsted acids and bases. Lewis acids are chemical species that can receive a pair of electrons from a Lewis base. Lewis bases are chemical species that can donate a pair of electrons to a Lewis acid. Lewis acids that can be used in the practice of this disclosure include tin carboxylates such as dibutyl tin dilaurate (DBTDL), dimethyl hydroxy tin oleate, dioctyl tin maleate, di-n-butyl tin maleate, dibutyl tin diacetate , dibutyl tin dioctoate, stannous acetate, stannous octoate, and various other organometallic compounds such as lead naphthenate, zinc caprylate and cobalt naphthenate. DBTDL is a preferred Lewis acid. Lewis bases that can be used in the practice of this disclosure include, but are not limited to, primary, secondary and tertiary amines. These catalysts are typically used in moisture curing applications.
    [0053] Bronsted acids are chemical species that can lose or donate a hydrogen ion (proton) to a Bronsted base. Bronsted bases are chemical species that can gain or receive a hydrogen ion from a Bronsted acid. Bronsted acids that can be used in the practice of this disclosure include, for example, sulfonic acid.
    [0054] In the practice of this disclosure, the minimum amount of crosslinking catalyst used is a catalytic amount. Typically, this amount is at least 0.01, preferably at least 0.02 and more preferably at least 0.03 percent by weight (% by weight) of the combined weight of ethylene/vinyl silane polymer and catalyst. The maximum amount of crosslinking catalyst in the ethylene polymer is imposed only for economy and feasibility (e.g., decreasing returns), but typically an overall maximum comprises less than 5, preferably less than 3 and more preferably less than 2% by weight of the combined weight of ethylene polymer and condensation catalyst. Liquid polymer modifier
    [0055] The crosslinkable blend includes a liquid polymer modifier. As used herein, a "liquid polymer modifier" is a non-functionalized plasticizer (NFP). When used herein, an "NFP" is a liquid hydrocarbon, which does not include, to an appreciable extent, functional groups selected from hydroxy groups, aryl and substituted aryl groups, halogens, alkoxy groups, carboxylates, esters, carbon unsaturation, acrylates, oxygen , nitrogen, and carboxyl. The term "appreciable extent" means that these groups and compounds comprising these groups are not deliberately added to the NFP, and if present at all, are present in incorporations in amounts less than 5 percent by weight of the NFP, or in amounts less than 4, 3, 2, 1, 0.7, 0.5, 0.3, 0.1, 0.05, 0.01, or 0.001% by weight, based on the weight of the NFP.
    [0056] In an embodiment, aromatic moieties (including any compound whose molecules have characteristic ring structure of benzene, naphthalene, phenanthrene, anthracene, etc.) are substantially absent in NFP. In another embodiment, naphthenic moieties (including any compound whose molecules have a saturated ring structure that would be produced by hydrogenating benzene, naphthalene, phenanthrene, anthracene, etc.) are substantially absent from the NFP. The expression "substantially absent" means that these compounds are not deliberately added to the compositions and if present at all, are present in amounts less than 0.5% by weight, preferably in amounts less than 0.1% by weight of the NFP.
    [0057] In another embodiment, NFP does not contain olefinic unsaturation to any appreciable extent. "Appreciable extent of olefinic unsaturation" means that the carbons involved in olefinic bonds account for less than 10% of the total number of carbons in the NFP, preferably less than 8%, 6%, 4%, 2%, 1%, 0, 7%, 0.5%, 0.3%, 0.1%, 0.05%, 0.01%, or 0.001%. In some embodiments, the percentage of NFP carbons involved in olefinic bonds is between 0.001 and 10% of the total number of carbon atoms in the NFP, preferably between 0.01 and 5%, preferably between 0.1 and 2%, most preferably between 0.1 and 1%.
    [0058] In one embodiment, the liquid polymer modifier is an NFP which is a phthalate-free hydrogenated C8 to C12 poly-alpha-olefin. Phthalate-free hydrogenated C8 to C12 poly-alpha olefin is naturally inert and does not affect the curing chemistry of the crosslinkable mixture as do conventional modifiers such as mineral oil, white oil and paraffinic oils. Similarly, the present liquid polymer modifier does not affect other chemistries, such as, for example, antioxidant chemistry, charge chemistry, adhesion chemistry, or the like.
    [0059] Furthermore, the present liquid polymer modifier has high permanence, good compatibility with polyethylenes and ethylene copolymers, and narrow molecular weight distribution (Mw/Mn or MWD). As a result, applications using the present liquid polymer modifier have a surprising combination of desired properties including high cure efficiency, better flexibility and toughness, and easy processing. Such applications exhibit excellent surface properties and exceptional retention of properties over time.
    [0060] A non-limiting example of a suitable liquid polymer modifier is a polymer modifier sold under the trade name ELEVAST, such as ELEVAST R-150. ELEVAST polymer modifier is available from ExxonMobil Chemical Company, Houston, Texas.
    [0061] The liquid polymer modifier advantageously replaces extender oils (paraffin oil and/or mineral oil) in the molded article under crosslinked melting. When compared to the same thinning oil crosslinked melt molded article, a crosslinked melt molded article containing the present liquid polymer modifier exhibits improved softness (i.e., lower Shore A hardness value), increased flexibility (i.e., increases in M100), greater elongation, improved elasticity, and improved processability (lower viscosity)—all without decreasing the dielectric strength of the cross-fused cast article. The above physical improvements from the liquid polymer modifier are surprising and unexpected over extender oils because extender oils lower the dielectric strength of the resulting crosslinked product. Non-limiting applications of crosslinked melt molded article containing the present liquid polymer modifier and exhibiting the above physical improvements (no loss of dielectric strength) include wire and cable, and other applications where good dielectric properties are required.
    [0062] The liquid polymer modifier can be added during different steps of the production process. In one embodiment, the liquid polymer modifier is added in a crosslinkable mixture composed of (1) organopolysiloxane (with two or more hydroxyl end groups) and (2) silane grafted or silane copolymerized polyolefin. This crosslinkable mixture is subsequently melt molded, partially crosslinked, cooled, and further crosslinked during exposure to ambient conditions.
    [0063] In one embodiment, the liquid polymer modifier is added to a crosslinkable mixture composed of (1) organopolysiloxane containing two or more hydroxyl end groups, (2) polyolefin (3) silane, and (4) peroxide. This crosslinkable mixture is subsequently melt molded, partially crosslinked, cooled, and further crosslinked when exposed to ambient conditions.
    [0064] In one embodiment, the liquid polymer modifier is added with the crosslinking catalyst. A silane-grafted polyolefin is prepared to which a hydroxyl terminated polydimethylsiloxane is added. The mixture is melt molded into a storage article. The storage article is introduced into a second melt molding step in which the storage article is melt molded into a finished article. The process includes introducing the crosslinking catalyst and liquid polymer modifier during or after the second melt molding operation. The process further includes cooling and crosslinking the finished article from the second melt molding step. Loads and Additives
    [0065] The composition from which the crosslinked article is prepared, for example, protective jacket or cable insulation layer, injection molded elastomeric connector, etc., or other article of manufacture, for example, seal, gasket, sole of shoe, etc., may or may not have cargo. If it has charge, then the amount of charge present preferably should not exceed an amount that would cause unacceptably great degradation of the electrical and/or mechanical properties of the crosslinked composition. Typically, the amount of filler present is between 2 and 80, preferably between 5 and 70 percent by weight (% by weight), based on the weight of polymer. Representative fillers include kaolin clay, magnesium hydroxide, silica, calcium carbonate and carbon black. The charge may or may not have flame retardant properties. In a preferred embodiment of this disclosure in which a filler is present, the filler is coated with a material that will prevent or retard any tendency the filler might otherwise have to interfere with the silane curing reaction. An example of such a filler coating is stearic acid. Load and catalyst are selected to avoid any unwanted interactions and reactions, and this selection is well within the technician's usual experience.
    The compositions of this invention may also contain additives such as, for example, antioxidants (for example, hindered phenols such as, for example, IRGANOX™ 1010 a registered trademark of Ciba Specialty Chemicals), phosphites (for example, IRGAFOS™ 168 a registered trademark of Ciba Specialty Chemicals), UV stabilizers, adhesion additives, light stabilizers, (such as hindered amines), plasticizers (such as dioctyl phthalate or epoxidized soybean oil), pre-vulcanization inhibitors, mold release agents , sticking agents (such as hydrocarbon sticking agents), waxes (such as polyethylene waxes), processing aids (such as oils, organic acids such as stearic acid, metallic salts of organic acids), extender oils (such as such as paraffin oil and mineral oil), dyes or pigments to the extent that they do not interfere with the desired physical or mechanical properties of the compositions of the present invention. These additives are used in amounts known to those skilled in the art.
    [0067] The crosslinkable mixture may comprise two or more embodiments disclosed herein. Combination/Manufacturing
    [0068] The combination of silane-functional ethylene polymer, polyfunctional organopolysiloxane, liquid polymer modifier, free radical initiator, optional crosslinking catalyst, optional charge and optional additives, if any, can be performed by standardized means known to those skilled in the art in technique. Examples of combination equipment are: internal batch mixers such as Banbury or Bolling internal mixer. Alternatively, continuous single or twin screw mixers can be used, such as a Farrel continuous mixer, a Werner and Pfleiderer twin screw mixer, or a Buss continuous kneading extruder. The type of mixer used, and the operating conditions of the mixer will affect composition properties such as viscosity, volumetric resistivity, and smoothness of the extruded surface.
    Typically, the components of the composition are mixed at a temperature and for a time sufficient to completely homogenize the mixture, but insufficient to gel the material. Typically, the catalyst is added to the ethylene/vinyl silane polymer, but it can be added before, with or after additives, if any. Typically, the components are mixed in a melt mixing device. Then, the mixture is molded into the final article. The article blending and fabrication temperature must be above the melting point of the ethylene/vinyl silane polymer, but below 250°C.
    [0070] In some embodiments, either or both of the crosslinking catalyst and additives are added as a masterbatch. Such masterbatch mixtures are commonly formed by dispersing catalyst and/or additives in an inert plastic resin, eg, low density polyethylene. Conveniently, standard blends are formed by melt compounding methods.
    [0071] In an embodiment, one or more of the components are dried before combining them, or a mixture of components is dried after compounding, to reduce or eliminate potential pre-vulcanization that can be caused by moisture present in or associated with the component , for example, cargo. In one embodiment, crosslinkable silicone modified polyolefin blends are prepared in the absence of a crosslinking catalyst to extend shelf life, and the crosslinking catalyst is added as a final step in preparing a melt molded article.
    [0072] In one embodiment, the disclosure is a process for manufacturing crosslinked melt molded articles, the process comprising the steps of: (A) Forming a crosslinkable mixture comprising: (1) Organopolysiloxane containing two or more terminal functional groups (such as as hydroxyl end groups) and (2) Polyolefin grafted with silane or copolymerized with silane; (B) Melt molding and partially crosslinking the mixture into an article; and (C) Cool and continue crosslinking the article.
    [0073] The process does not require the use of external post molding heat and/or moisture although one or both may be used if desired. Crosslinking can be promoted by adding a catalyst to the mixture before or during melt molding, or to the melt molded article (e.g., by diffusion from a contiguous layer if the article is a layer in a multilayer structure). Surprisingly, composing a mixture containing these components produces a stable thermoplastic composition which can be molded and partially crosslinked by melt processing into an article, but during storage at ambient conditions undergoes complete crosslinking without the need for external heat or moisture. On a microscopic scale, the morphology of such a mixture shows greater compatibility between the silicone and polyolefin phases when compared with a physical (unreacted) silicone/polyolefin mixture or with a physical, i.e., unreacted, mixture of a siloxane and a silane-grafted polyolefin.
    [0074] The process of this disclosure eliminates the reliance on external moisture diffusion that is required in conventional moisture curing. The process of this disclosure is particularly useful for fabricating thick-walled lattice structures (greater than 0.2 millimeters (mm), more typically greater than 0.5 mm and even more typically greater than 1 mm), such as in cable insulation. high and medium voltage, molded elastomeric wire and cable fittings and connectors, and heat resistant molded automotive parts. In the case of injection molded parts, after injection into a mold and once the article is formed, the articles do not require additional heating or waiting times to cure. In fact, the article can be cooled to achieve green strength to retain the desired shape during removal from the mold. Once removed from the mold, the curing step continues outside the mold to achieve complete cure. This approach improves manufacturing cycle time and achieves higher productivity (units per time).
    [0075] In one embodiment, hydroxyl-terminated organopolysiloxane reacts with an alkoxysilane (or silanol) that is grafted onto a polyolefin or other polymer. Methods for preparing such grafted polymers are well known. For example, one can graft vinyl trimethoxysilane (VTMS) onto polyethylene using peroxide. Also, various reactor copolymers are obtainable, such as SI-LINK™, which is a copolymer of VTMS and ethylene obtainable from The Dow Chemical Company.
    [0076] In one embodiment, the disclosure is a process for making crosslinked melt molded articles, the process comprising the steps of: (A) Forming a crosslinkable mixture comprising: (1) Organopolysiloxane containing two or more end functional groups; (2) Polyolefin; (3) Alkoxysilane; and (4) Peroxide; (B) Melt molding the mixture into an article under conditions sufficient to graft the alkoxysilane to the polyolefin and to partially crosslink the silane-grafted polyolefin; and (C) Cool and continue crosslinking the article. This incorporation combines the grafting of silane onto the polyolefin and the initiation of crosslinking the mixture in a single step.
    [0077] In one embodiment, the disclosure is a process for manufacturing crosslinked melt molded articles, the process comprising the steps of: (1) preparing a silane-grafted polyolefin; (2) blending the silane-grafted polyolefin with a hydroxyl terminated polydimethylsiloxane; (3) melt molding the mixture into a storage article; (4) introducing the storage article into a second melt molding step in which the storage article is melt molded into a finished article; (5) introducing a crosslinking catalyst during or after the second melt molding operation; and (6) cooling and crosslinking the finished article from the second melt molding step.
    [0078] This incorporation allows the decoupling of the mixing forming steps of the melt molding and crosslinking steps thus allowing the process to be carried out during different spaces and times. Typically, the storage article is comprised of pellets that are remelted and optionally mixed with a crosslinking catalyst to form the finished molded or extruded article. Polysiloxane bond
    Without being bound by theory, it is believed that the crosslinkable mixture forms unique polysiloxane bonds between polymer chains of the polyolefin when the mixture is subjected to a melt forming or melt molding procedure. It is believed that during melt molding, the hydroxyl-terminated organopolysiloxane reacts with the alkoxysilane (or silanol) that is grafted onto the polyolefin to form a polysiloxane bond between at least two individual polymer chains of the polyolefin. The polysiloxane linkage has the structure (I) below.

    [0080] The value of n is from 1 to 100,000. The term "n" can have a lower limit of 1, or 2, or 3, or 4, or 5, or 10, or 15, or 20 and an upper limit of 50, or 75, or 100, or 120, or 400, or 1000, or 100,000.
    [0081] The polysiloxane (I) bond is unique compared to bonds formed by conventional peroxide crosslinking and/or silane grafting/conventional moisture cure. Conventional silane-crosslinked polyolefin contains a "-Si-O-Si-" bond between polymer chains. On the other hand, the present polysiloxane linkage of structure (I) has a minimum of three (3) silicon atoms between polymer chains. Applicants have found that the single polysiloxane (I) bond surprisingly results in a composition showing greater compatibility between polyolefin and silicone than would be obtained in a physical blend of silicone and polyolefin as demonstrated in Figures 4 and 5. Not bound by any particular theory , the hydroxyl terminated organopolysiloxane which reacted with the silane-grafted polyethylene in the presence of a catalyst surprisingly improves the compatibility of the organopolysiloxane (i.e., PDMS) component within the polyolefin resulting in a single-phase morphology.
    [0082] Figures 4A (250X) and 4B (500X) are electron micrographs of prepared blends of polyethylene grafted with VTMS mixed with hydroxy terminated polydimethylsiloxane (PDMS). Immiscible silicone is visible as discrete and distinct domains within the polyethylene matrix. Unbound by any theory, immiscible silicone is believed to be unreacted (ie, uncrosslinked) silicone.
    [0083] Figures 5A (250X) and 5B (500X) show cross-linked polyethylene prepared by means of the present process that uses hydroxyl-terminated organopolysiloxane and avoids moisture curing. Figures 5A and 5B show electron micrographs of VTMS grafted polyethylene blended with hydroxy terminated polydimethylsiloxane in the presence of a catalyst and crosslinked in accordance with an embodiment of the present disclosure.
    [0084] Present in the cross-linked polyethylene of Figures 5A and 5B are polysiloxane bonds of structure (I) connecting polyethylene chains. The micrographs of Figures 5A and 5B show uniform morphology — evidence of the improved compatibility between the hydroxyl-terminated organopolysiloxane and polyethylene due to incorporation of the silicone in the structure bond (I). The formation of the polysiloxane (I) bond does not require moisture (i.e., water) as is required in conventional moisture curing. articles of manufacture
    [0085] In one embodiment, the composition of this disclosure can be applied to a cable as an insulating or coating layer in known amounts and by known methods (for example, with the equipment and methods described in USP 5,246,783 and 4,144,202). Typically, the composition is prepared in a reactor/extruder equipped with a cable coating die and after formulating the composition components, the composition is extruded onto the cable when the cable is drawn through the die. Curing can start in the reactor/extruder.
    [0086] One of the benefits of this disclosure is that the melt-molded article does not require post-treatment, for example, after demolding or passing through a molding matrix, under curing conditions, for example, temperature above room temperature and /or moisture from an external source such as a water bath or “sauna”. Although not necessary or preferred, the molded article may be exposed to one or both of elevated temperature and external humidity and if exposed to an elevated temperature, it will typically be between ambient temperature and elevated temperature, but below the melting point of the polymer for a period of time such that the article achieves a desired degree of crosslinking. The temperature of any post mold cure must be above 0°C.
    [0087] Other articles of manufacture that can be prepared from the polymeric compositions of this invention include fibers, bands, sheets, tapes, tubes, pipes, sealing strips, seals, gaskets, hoses, foams, shoes and fans. These articles can be manufactured using known equipment and techniques.
    [0088] The melt-molded article may comprise two or more embodiments disclosed herein.
    [0089] By way of example, and not by way of limitation, examples of the present disclosure will now be provided. Unless stated otherwise, all parts and percentages are by weight. Examples Example 1
    [0090] Table 1 shows the evaluation of various compositions. The ENGAGE™ 8200 plastomer (an ethylene/octene copolymer of MI equal to 5, density 0.870 g/cm3 in solid pellets) is used in the experiments. The polymer pellets are heated at 40°C for two hours, then mixed in a rotating drum with a mixture of VTMS and LUPEROX 101 peroxide (2,5-dimethyl-2,5-di(tertiobutyl peroxy)hexane obtainable from Arkema) and allowed to soak in a glass container using container cylinder until the pellets are visibly dry.
    [0091] A Brabender batch mixer (250 g) is used to graft VTMS into the polymer. The combination is carried out at 190°C for 15 minutes. The grafted polymer is pressed onto a plate at room temperature and sealed in a thin foil bag for subsequent experiments with polydimethylsiloxane (PDMS).
    [0092] A Brabender mixer (45 cm3) is used to combine the grafted resin, silanol terminated PDMS and catalyst. The combination is carried out at an adjusted temperature of 150°C as follows. First, the mixer was loaded with ENGAGE 8200 grafted with VTMS, melted and mixed for 2 minutes at 45 rpm. The silanol terminated PDMS (GELEST DMS-S15) is gradually added over a period of approximately 3 minutes and after the addition is complete, the mixture is further mixed for 2 minutes at 45 rpm. Catalysts (DBTDL, sulfonic acid or blend) are then added and mixed for 15 minutes at 45 rpm. If the resulting compound is thermoplastic, i.e. no significant crosslinking is visible, it is pressed into an approximately 1.3mm board immediately after removal from the blender and stored overnight in a sealed 25° aluminum foil bag. Ç.
    [0093] Afterwards, the samples are cut to analyze curing via hot deformation analysis (oven at 200°C, 15 minutes). The percentage of elongation under load of 20 N/mm2 is then measured. A common pattern for proper crosslinking is elongation less than or equal to 100%. Measurements are taken on triple samples. Table 1 - Hot deformation test results of test compositions

    *Since the sample cross-linked prematurely, the catalyst level was subsequently reduced as described in later examples.
    [0095] Si-g-PE is the ENGAGE 8200 plastomer grafted with silane.
    [0096] Sil-PDMS is silanol terminated PDMS GELEST DMS-S15.
    [0097] Sulfonic acid is B-201 obtainable from King Industries.
    [0098] DBTDL is FASTCAT 4202 dibutyl tin dilaurate.
    [0099] Percent elongation is measured from hot deformation test at 200°C, load of 0.2 MPa maintained for 15 minutes per IEC 60811-2-1.
    [0100] The strain test results in Table 1 show that the addition of PDMS to either the base resin (sample A, a control) or the silane-grafted resin (sample C) does not produce the desired crosslinking. Additional comparative examples (samples B and F), which represent conventional moisture curing systems, failed the hot deformation test after overnight storage without any exposure to external moisture (except that which may have been trapped during compounding or in the storage bag). Inventive samples D and E in which OH-terminated PDMS is added to a grafted resin and further reacted with a catalyst produce effective crosslinking either immediately during the compounding step in the mixer (sample D) or produced a thermoplastic compound, which can be molded in a formed article (eg a plate) and when stored overnight in a sealed bag produced a homogeneous crosslink as shown by sample E. This is the desired result.
    [0101] The data also show that it is possible to design compositions that can be homogeneously mixed to produce a thermoplastic material that exhibits excellent crosslinking without the need for exposure to external moisture that is desirable for thick articles such as molded parts or medium cable sheathing voltage or high voltage.
    [0102] As an additional confirmation of crosslinking, the composition of sample E is repeated in another experiment where the prepared sample is subjected to a DMA analysis, with a temperature scan from -150°C to 200°C. As the data in the Figure show, compared to ENGAGE 8200 base resin (melting point approx. 70°C), the modulus of the reactively modified PDMS/ENGAGE blend displays a plateau before the melting point, indicating a good temperature resistance compared to base resin.
    [0103] Electron microscopy shows dramatically improved phase compatibility. For example, sample E shows a predominantly single homogeneous phase with some finely dispersed silicone domains. In contrast, other compositions tested (samples A and C) show typical morphologies of very immiscible systems containing large and distinct silicone domains visible as droplets within the polyolefin matrix. Example 2
    [0104] The data shown in Table 2 compare an LLDPE resin (MI 0.7, density 0.920 g/cm3) grafted with 2% VTMS in the presence of 3% silanol terminated polydimethylsiloxane (OH-PDMS) against a control sample grafted under the same conditions without the OH-PDMS. Both materials were first dried and then extruded onto a wire (124 milliinch yarn OD, 30 milliinch wall thickness) in the presence of a tin catalyst. The insulation is removed, cured for 16 hours at ambient conditions (23°C and 70% relative humidity), and then subjected to a hot deformation test (200°C, 15 min, 15 N/m2). The results show that the comparative composition does not achieve 100% hot set elongation and 10% hot elongation targets. On the other hand, the inventive composition passes the hot deformation and hot elongation tests. The data demonstrates that with disclosure, the rapid cure rate was achieved in ambient conditions. Table 2 - Results of hot deformation and hot elongation tests of test compositions
    Example 3
    [0105] The dataset for this example is obtained from a sample taken from a molded part. The molded part 10 (Figure 2) comprises an insulating layer 11 which comprises an elastomer resin system which is grafted with vinyl trimethoxysilane in the presence of OH-PDMS. The molded part 10 is a 35 KV prototype connector comprising the insulating layer 11 sandwiched between an outer semiconductor layer (12) and an inner semiconductor layer (13). The insulating layer 11 comprises a composition of this disclosure. The semiconductor layers are first molded separately and cured by peroxide in a first molding step, then assembled together in a second mold where the insulating layer is injected between them. The insulating compound is pre-mixed with a standard tin catalyst mixture, injection is carried out in a fully thermoplastic mode, and the part is demolded after cooling (molding time 1-5 minutes depending on test time). The inner semiconductor layer 13 is approximately 4 mm thick and covers most of the insulation, except with respect to the edges. The outer semiconductor layer 12 is approximately 3.5 mm thick and covers the entire insulating layer, ie no external exposure, and the insulating layer 11 itself is approximately 11.6 mm thick. Once received from the molding shop, the part is cut and three samples are taken from the middle section of the insulating layer for DMA testing. All samples are 1.9 mm thick. Starting from the outer edge of the insulating layer, Sample 1 is about 3 mm inside the layer, Sample 2 is about 5 mm inside the layer, and Sample 3 is about 7 mm inside the layer. The part is handled under normal conditions of transport and laboratory storage prior to testing, ie, no special exposure to heat and moisture. The data in Figure 3 shows a plateau modulus at a temperature above the melting point of each of the samples, or in other words, complete curing of the material. Example 4
    [0106] Insulation materials, sample 2, sample 5 and sample 6 are prepared via reactive extrusion in a ZSK-30 twin screw extruder. • Sample 2 does not contain any flexibility modifiers. • Sample 5 is modified with paraffinic oil (SUNPAR 2280, Sunoco Corp.). • Sample 6 is modified with liquid polymer modifier (ELEVAST R150, ExxonMobil Corp.).
    [0107] Samples 2, 5, and 6 are melt blended with a standard mixture of tin catalyst at 5% level in a 250 cm3 Brabender at 150°C, 35 rpm, 10 min.
    [0108] - Plates are prepared via compression molding at 170°C for 5 min; the plates are press cooled and removed from the mold.
    [0109] - The plates are cured in a controlled environmental chamber for 3 days at ambient conditions (23°C and 70% relative humidity (RH).
    [0110] - Cured boards are tested for mechanical and electrical properties shown in Table 3.

    [0111] Alternating current breaking strength (ACBD) is the minimum alternating current voltage that causes a portion of a material (such as an insulator) to become electrically conductive. ACBD is determined according to ASTM D 149 (kV/mm).
    [0112] Non-limiting examples of the present disclosure are provided below. E1. A crosslinkable mixture is provided which includes a polyolefin, an alkoxysilane, an organopolysiloxane containing two or more hydroxyl end groups, a free radical initiator, and a liquid polymer modifier. The crosslinkable mixture, according to E1, characterized by forming polysiloxane bonds between the polymer chains of the polyolefin when the crosslinkable mixture is melt molded into an article, the polysiloxane bonds having the structure (I):
    (I) where n=1 to 100,000.
    [0113] E3. The crosslinkable mixture according to E2, characterized in that it forms additional polysiloxane bonds of structure (I) when the melt-molded article is exposed to room temperature. E4. The crosslinkable mixture, according to any one of E1-E3, characterized in that it comprises a crosslinking catalyst. E5. The crosslinkable mixture, according to any one of E1-E4, characterized in that the polyolefin is a polyethylene. E6. The crosslinkable mixture according to any one of E1-E5, characterized in that it comprises a first polyethylene crosslinked to a second polyethylene by means of a polysiloxane linkage (I). E7. The crosslinkable mixture, according to any one of E1-E6, characterized in that the alkoxysilane is vinyl trimethoxysilane. E8. The crosslinkable mixture, according to any one of E1-E7, characterized in that the organopolysiloxane is hydroxyl-terminated polydimethylsiloxane. E9. The crosslinkable mixture according to any one of E1-E8, characterized in that the liquid polymer modifier is a non-functionalized plasticizer comprising a phthalate-free hydrogenated C8C12 poly-alpha-olefin.
    [0114] Another crosslinkable blend (E10) is provided which includes a silane-grafted polyethylene, an organopolysiloxane containing two or more hydroxyl end groups, and a liquid polymer modifier. E11. The crosslinkable mixture, according to E10, characterized in that it forms a crosslinked polymeric composition comprising polysiloxane bonds between the polymer chains of the polyolefin when the crosslinkable mixture is melt-molded into an article, the polysiloxane bonds having the structure (I)
    where n=1 to 100,000.
    [0115] E12. A melt molded article is provided which includes a cross-linked polyethylene composition comprising polysiloxane linkages between the polymer chains of the polyethylene, the polysiloxane linkages having the structure (I)
    where n=1 to 100,000; and a liquid polymer modifier. E13. The melt-molded article according to E12, characterized in that it comprises a first polyethylene which is cross-linked to a second polyethylene by means of the polysiloxane linkage of structure (I). E14. The melt-molded article according to any one of E12-E13, characterized in that it is selected from the group consisting of an insulating layer, a cable jacket, and an electrical power cable.
    [0116] E15. An insulating layer of an electrical cable is provided, characterized in that it comprises a cross-linked polyethylene composition comprising polysiloxane bonds between the polyethylene chains, the silane bonds having the structure (I):
    where n=1 to 100,000, a liquid polymer modifier, and the insulating layer has an ACDB value greater than 34 kV/mm measured in accordance with ASTM D 149. E16. Insulating layer, according to E15, characterized by the fact that the ACBD value is greater than 34 kV/mm to 42 kV/mm.
    [0117] E17. A melt molded article characterized by comprising a cross-linked polyethylene composition, an organopolysiloxane containing two or more hydroxyl end groups, and a liquid polymer modifier is provided. E18. The melt-molded article, according to E17, characterized in that the organopolysiloxane containing two or more hydroxyl end groups is hydroxyl-terminated polydimethylsiloxane. E19. The molded article according to any one of E17-E18, characterized in that it comprises a crosslinking catalyst. E20. The molded article according to any one of E17-E19, characterized in that it comprises polysiloxane bonds between the polyethylene chains, the polysiloxane bonds having the structure (I)
    where n=1 to 100,000. E21. The molded article according to any one of E17-E20, characterized in that it is selected from the group consisting of an insulating layer, a cable jacket, and an electrical power cable. [0118] Although the invention has been described in considerable detail through the foregoing specific embodiments, these details are primarily for illustrative purposes. One skilled in the art can make many variations and modifications without departing from the spirit and scope of the invention described in the following claims. 1/2
    权利要求:
    Claims (9)
    [0001]
    1. Crosslinkable mixture, characterized by the fact that it comprises: a polyolefin; an alkoxysilane comprising an ethylenically unsaturated hydrocarbyl group; an organopolysiloxane containing two or more hydroxyl end groups; an initiator via free radicals; and a liquid polymer modifier, which is a non-functionalized plasticizer comprising a phthalate-free hydrogenated C8-C12 poly-alpha-olefin.
    [0002]
    2. Crosslinkable mixture, according to claim 1, characterized in that it comprises a crosslinking catalyst.
    [0003]
    3. Crosslinkable mixture, according to any one of claims 1 or 2, characterized in that the polyolefin is a polyethylene.
    [0004]
    4. Crosslinkable mixture, according to any one of claims 1 to 3, characterized in that the alkoxysilane is vinyl-trimethoxy-silane.
    [0005]
    5. Crosslinkable mixture, according to any one of claims 1 to 4, characterized in that the organopolysiloxane is hydroxyl-terminated polydimethylsiloxane.
    [0006]
    6. Crosslinkable mixture, characterized by the fact that it comprises: a polyethylene grafted with silane; an organopolysiloxane containing two or more hydroxyl end groups; and a liquid polymer modifier which is a non-functionalized plasticizer comprising a phthalate-free hydrogenated C8-C12 poly-alpha-olefin.
    [0007]
    7. Crosslinkable mixture, according to claim 6, characterized in that it comprises a 2/2 crosslinking catalyst.
    [0008]
    8. Fusion molded article, characterized in that it comprises: a cross-linked polyethylene composition; an organopolysiloxane containing two or more hydroxyl end groups; and a liquid polymer modifier which is a non-functionalized plasticizer comprising a phthalate-free hydrogenated C8-C12 poly-alpha-olefin.
    [0009]
    9. Fusion-molded article according to claim 8, characterized in that it comprises polysiloxane bonds between the polymer chains of polyethylene, the polysiloxane bonds having the structure (I): where n=1 to 100,000.
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    法律状态:
    2020-10-20| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-10-20| B25A| Requested transfer of rights approved|Owner name: UNION CARBIDE CORPORATION (US) |
    2020-10-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-11| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 11/05/2021, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US24285709P| true| 2009-09-16|2009-09-16|
    US61/242,857|2009-09-16|
    PCT/US2010/048727|WO2011034838A1|2009-09-16|2010-09-14|Crosslinked, melt-shaped articles and compositions for producing same|
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