Method for producing a homogeneous mixture of polyolefin solids and liquid additives

Abstract

A method for producing a homogeneous mixture of polyolefin solids and liquid additives without melting the polyolefin solids during production, comprising applying acoustic energy at a frequency of 20 to 100 hertz to a heterogeneous mixture comprising the polyolefin solids and the liquid additives while maintaining the temperature of the heterogeneous mixture above the freezing point of at least one liquid additive and below the melting temperature of the polyolefin solids for a time sufficient to substantially mix the polyolefin solids and the liquid additives together, thereby producing a homogeneous mixture without melting the polyolefin solids.

Description

Technical Field

[0001] Mixing of polyolefin and additives.

[0002] Introduction Patents and patent application publications in or related to this field include US7,188,993B1, US7695,817B2, US8,124,309B2, US8,435,714B2, US8,680,177B2, US8,889,331B2, US9,223,236B2, US9,593,919B2, US9,926,427B2, US9,957,360B2. Non-patent publications in or related to this field include Assessment of extrusion-sonication process on flame retardant polypropylene by rheological characterization, by G. Sanchez-Olivares, et al. AIMS Materials Science, 2016; vol. 3, no. 2, pages 620 to 633, and ENHANCED DISPERSION OF PARTICLE ADDITIVE INTO POLYMERS USING TWIN SCREW EXTRUSION WITH ULTRASOUND ASSISTANCE, by K. Tarverdi, et al., SPE ANTEC Anaheim 2017, pages 1058 to 1062.

[0003] Previous mixing methods rely on the mechanical blending of polyolefin solids (e.g., in a stirred tank apparatus) or melts (e.g., in a twin screw extruder apparatus) with liquid additives.

Summary of the Invention

[0004] We have discovered a method for producing a homogeneous mixture of a polyolefin solid and a liquid additive without melting the polyolefin solid during production. The method involves applying acoustic energy at a frequency of 20 to 100 Hertz to a heterogeneous mixture containing the polyolefin solid and the liquid additive for a time sufficient to substantially mix (thoroughly or completely homogenize) the polyolefin solid and the liquid additive together, while maintaining the temperature of the heterogeneous mixture above the freezing point of at least one of the liquid additives and below the melting temperature of the polyolefin solid, thereby producing a homogeneous mixture without melting the polyolefin solid.

DETAILED DESCRIPTION OF THE INVENTION

[0005] A method for producing a homogeneous mixture of a polyolefin solid and a liquid additive without melting the polyolefin solid during production. The method involves applying acoustic energy at a frequency of 20 to 100 Hertz (Hz) to a heterogeneous mixture containing the polyolefin solid and the liquid additive for a time sufficient to substantially mix (thoroughly or completely homogenize) the polyolefin solid and the liquid additive together, while maintaining the temperature of the heterogeneous mixture above the freezing point of at least one of the liquid additives and below the melting temperature of the polyolefin solid (and optionally, while maintaining the temperature of the homogeneous mixture produced therefrom), thereby producing a homogeneous mixture without melting the polyolefin solid. The method may further include the feature of not including solidifying the liquid additive. The method may further include the limitation that the heterogeneous mixture is not mechanically agitated (mixed by mechanical means) during the step of applying the acoustic energy.

[0006] Additional inventive aspects follow and, for ease of reference, several of the following are numbered.

[0007] Aspect 1. A method of producing a homogeneous mixture of a polyolefin solid and a liquid additive without melting the polyolefin solid during production, the method comprising applying acoustic energy at a frequency of 20 to 100 Hertz (Hz) to a first heterogeneous mixture comprising at least one liquid additive and a polyolefin solid for a time and at an acoustic intensity effective to substantially mix the at least one liquid additive and the polyolefin solid together while maintaining the temperature of the first heterogeneous mixture above the freezing point of the at least one liquid additive and below the melting temperature of the polyolefin solid (and optionally while maintaining the temperature of the homogeneous mixture produced therefrom), thereby producing a first homogeneous mixture comprising a polyolefin solid and at least one liquid additive without melting the polyolefin solid. The method may include not including solidifying the at least one liquid additive. The method may further include the feature of not mechanically moving the polyolefin solid or the heterogeneous mixture during the applying step. Each of the at least one liquid additives has a freezing point of less than 20.0 °C, or less than 15 °C, or less than 5 °C. The freezing point of each of the at least one liquid additives may independently be at least -80 °C, or at least -50 °C, or at least -10 °C. The polyolefin solid may have a melting temperature at which melting begins or starts that is 60 °C or higher, or higher than 100 °C, or higher than 110 °C. The polyolefin solid may have a melting temperature at which melting ends or is completed that is at most 220 °C, or at most 180 °C, or at most 150 °C.

[0008] Aspect 2. The method of Aspect 1, wherein the application step is characterized by any one of features (i) to (v): (i) the frequency is 50 to 70 Hz, or 55 to 65 Hz, or 58 to 62 Hz, or 59 to 61 Hz; (ii) the time is 0.5 minutes to 4 hours, or 0.5 minutes to 2 hours, or 1 minute to 60 minutes; (iii) both (i) and (ii); (iv) maintaining the temperature of the first heterogeneous mixture below the melting temperature of the polyolefin solid includes maintaining the temperature of the first heterogeneous mixture at 10 to 109 °C, or 15 to 99 °C, or 20.0 to 39.9 °C, or 20.0 to 29.9 °C (e.g., 25 °C ± 3 °C); (v) both (iv) and any one of (i) to (iii). The frequency is set by an acoustic mixer. The intensity is sufficient to move the material with an amplitude sufficient to be effective for mixing.

[0009] Aspect 3. The method of Aspect 1 or 2, wherein the polyolefin solid of the first heterogeneous mixture is characterized by a physical form (i.e., solid particle form) that is powder, granule, or pellet, and a melting temperature that is 61 to 180 °C, or 90 to 180 °C, or 110 to 174 °C, or 120 to 180 °C, at least one liquid additive of the first heterogeneous mixture is characterized by a freezing point below 20 °C or a melting point of 20 to 99 °C, and the first heterogeneous mixture is maintained at a temperature above the freezing point or melting point of at least one liquid additive and below 110 °C during the application step. The polyolefin solid of the first heterogeneous mixture can be characterized by an average particle size of 10 to 500 particles per gram (ppg), or 11 to 80 ppg, or 20 to 40 ppg when measured by counting.

[0010] Aspect 4. A method according to any one of Aspects 1 to 3, wherein the polyolefin of the polyolefin solid (i.e., the particulate form of the polyolefin polymer) is (A) a polyethylene homopolymer, an ethylene / alpha-olefin copolymer, a (hydrolyzable silyl group)-functionalized polyethylene copolymer (HSG-FP copolymer), an ethylene / unsaturated carboxylic acid ester copolymer (e.g., an ethylene / vinyl acetate (EVA) copolymer or an ethylene / (meth)acrylic acid alkyl (EAA or EAM) copolymer), or any blend of two or more thereof. The polyolefin can be a (hydrolyzable silyl group)-functionalized polyethylene copolymer (HSG-FP copolymer).

[0011] Aspect 5. At least one liquid additive is additive (B) liq ~(I) liq :(B) liq A liquid silanol condensation catalyst (dibutyltin dilaurate or ethanesulfonic acid), (C) liq A liquid antioxidant (e.g., 2-methyl-4,6-bis(octylthiomethyl)phenol, e.g., IRGASTAB Cable KV 10), (D) liq A liquid colorant (e.g., a liquid dye), (E) liq A liquid scorch retardant, (F) liq A liquid stabilizer (UV stabilizer) for stabilizing a homogeneous mixture against the effects of ultraviolet light, such as a liquid hindered amine light stabilizer (HALS), (G) liq A liquid processing aid (e.g., mineral oil), (H) liq A liquid flame retardant (e.g., brominated polystyrene, brominated rubber, poly(brominated vinyl), poly(brominated vinylidene), poly(brominated alkyl acrylate), poly(brominated alkyl acrylate), or brominated butadiene-styrene copolymer), and (I) liq Any one or more of liquid polymers other than (A) (e.g., polydimethylsiloxane fluid), a method according to any one of Aspects 1 to 4. (B) liq The liquid silanol condensation catalyst can be dibutyltin dilaurate or a (C1-C4) alkanesulfonic acid. (E) liqThe liquid scorch retarder can be 2,4-diphenyl-4-methyl-1-pentene (also known as alpha-methylstyrene dimer or AMSD) or a liquid hydrolyzable silane (e.g., octyltriethoxysilane (OTES) or vinyltrimethoxysilane (VTMS)). (E) liq can be a compound of the formula RSi(X)3, where R is (C1-C 10 ) alkyl, (C2-C 10 ) alkenyl, (C2-C 10 ) alkynyl, or X, and each X is independently (C1-C 10 ) alkoxy, (C1-C 10 ) carboxy, di((C1-C 10 ) alkyl)amino, or (C1-C 10 ) oximo. Alternatively or in addition, at least one liquid additive can be a liquid organic peroxide (e.g., tert-butyl peroxyacetate), a liquid crosslinking aid (e.g., triallyl isocyanurate), or a liquid moisture generator (e.g., hydroxyl-terminated polydimethylsiloxane fluid). The homogeneous mixture of embodiment 5 is moisture curable and can contain 15.00 to 99.99 weight percent (wt%) of (A) HSG-FP copolymer, based on the total weight of all the homogeneous mixture, with the balance being the liquid additive. In embodiment 5, the polyolefin of the polyolefin solid can be an (A) (hydrolyzable silyl group)-functionalized polyethylene copolymer (HSG-FP copolymer).

[0012] Embodiment 6. A method according to any one of embodiments 1 to 5, wherein the first heterogeneous mixture further comprises at least one particulate solid additive different from the polyolefin solid, and the first homogeneous mixture further comprises at least one particulate solid additive. The at least one particulate solid additive is a solid additive (B) sol ~(I) sol :(B) sol a solid silanol condensation catalyst (e.g., toluenesulfonic acid), (C) sol a solid antioxidant (e.g., 2,2'-thiobis(6-t-butyl-4-methylphenol) sold as LOWINOX TBP-6, (D) solSolid colorants (e.g., carbon black or TiO2), (E) sol Solid scorch retardants (e.g., hydroquinone), (F) sol Solid stabilizers (UV stabilizers) for stabilizing homogeneous mixtures against the effects of ultraviolet light, such as solid hindered amine light stabilizers (HALS) (e.g., poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]) sold as Chimassorb 944, (G) sol Solid processing aids (e.g., N,N’-ethylenebis(stearamide) sold as Kemamide W-40), (H) sol Solid flame retardants (e.g., metal hydrates), and (I) sol Can be any one of solid polymers other than (A) (e.g., polypropylene homopolymers or propylene / ethylene copolymers). Alternatively or in addition, at least one particulate solid additive can be a solid organic peroxide (e.g., dicumyl peroxide), a solid crosslinking aid (e.g., triallyl isocyanurate), or a solid moisture generator (e.g., aluminum trihydrate (Al2O3·3H2O) or calcium oxalate monohydrate). Each of the at least one particulate solid additive can have a melting temperature at which melting begins or starts that is higher than 20.0 °C, or higher than 100 °C, or higher than 200 °C. The at least one particulate solid additive can have a melting temperature at which melting ends or is completed that is up to 4,000 °C, or up to 2,000 °C, or up to 1,000 °C.

[0013] Aspect 7. Before the imprinting step, a contacting step (i) or (ii): (i) contacting a polyolefin solid with at least one liquid additive to produce a first heterogeneous mixture, or (ii) contacting the polyolefin solid with a low melting point solid additive having a melting point of 25 to 110 °C (e.g., triallyl cyanurate, m.p. 26 - 28 °C) to produce a heterogeneous solid premix, melting the low melting point solid additive without melting the polyolefin solid to produce a first heterogeneous mixture, the method according to any one of Aspects 1 - 6, further comprising producing a first heterogeneous mixture. The low melting point solid additive may have a melting point of 30.0 °C to 109 °C, or 40.0 °C to 79.9 °C, or 30.0 °C to 49.9 °C. The polyolefin solid used in contacting step (i) may not contain at least one liquid additive. The first heterogeneous mixture used in the step of applying acoustic energy may be freshly prepared. "Freshly prepared" means that the time between contacting step (i) or (ii) and the start of the step of applying acoustic energy is short enough to prevent at least one liquid additive, if possible, from passively soaking or absorbing to any significant extent or to any extent into the polyolefin solid for the length of time required. A sufficiently short time between the contacting step and the start of the step of applying acoustic energy can be less than 30 minutes, or less than 15 minutes, or less than 10 minutes, or less than 5 minutes. Alternatively, the first heterogeneous mixture used in the step of applying acoustic energy may be pre-aged. "Pre-aged" means that the time between contacting step (i) or (ii) and the start of the step of applying acoustic energy is long enough to allow at least one liquid additive, if possible, to passively soak or absorb some, but not all, of at least one liquid additive into the polyolefin solid to a significant or measurable extent for the length of time required. A sufficiently long time between the contacting step and the start of the step of applying acoustic energy can be at least 30 minutes, or more than 60 minutes, or more than 120 minutes.

[0014] Aspect 8. A step of contacting a first homogeneous mixture with at least one particulate solid additive different from the polyolefin solid to produce a second heterogeneous mixture comprising the first homogeneous mixture and the at least one particulate solid additive, and then applying acoustic energy at a frequency of 20 to 100 Hz and an acoustic intensity effective to mix them substantially together while maintaining the temperature of the second heterogeneous mixture above the freezing point of the at least one liquid additive and below the melting temperature of the polyolefin solid, thereby producing a second homogeneous mixture comprising the polyolefin solid, the at least one liquid additive, and the at least one particulate solid additive without melting the polyolefin polymer solid during the production step. The method according to any one of Aspects 1 to 7. The method may include not including solidifying the at least one liquid additive. The at least one particulate solid additive may be as described elsewhere herein.

[0015] Aspect 9. A method according to any one of Aspects 1 to 8, further comprising a step of melting the polyolefin solid of the homogeneous mixture to produce a molten mixture, a step of shaping the molten mixture to obtain a shaped molten mixture, and a step of cooling the shaped molten mixture to obtain a shaped solid. The shaped solid may be useful as a manufactured article. Shaping may include coating, extrusion, or molding. The homogeneous mixture may be the first or second produced homogeneous mixture depending on the numbered aspect.

[0016] Aspect 10. The forming step includes extruding the molten mixture as a coating onto a conductive core (e.g., a wire, an optical fiber, or both), solidifying the coating to produce a coated conductor including the conductive core and a coating-formed solid at least partially covering the conductive core, according to the method of Aspect 9. The method may further include curing (crosslinking) the coating-formed solid to provide a coated conductor including the conductive core and a coating-formed cured product at least partially covering the conductive core. This aspect can be used to produce manufactured articles including power cables such as low-voltage power cables.

[0017] Aspect 11. The method of Aspect 9 or 10 further includes curing the polyolefin of the formed solid to obtain a formed cured product.

[0018] Aspect 12. A formed cured product prepared by the method of Aspect 11.

[0019] The method produces a homogeneous mixture in an acoustic mixer device that does not include components that can interfere with or attenuate the acoustic energy of the applying step. Acoustic mixer devices for use on various scales from laboratory workbenches to commercial manufacturing are commercially available, including resonant acoustic mixers from Resodyn Acoustic Mixers, Butte, Montana, USA.

[0020] The production method produces a homogeneous mixture without melting the polyolefin solid. In a practical sense, achieving homogeneity can be recognized by visual inspection or by sampling the mixture when transitioning from a heterogeneous to a homogeneous state and measuring the characteristics of the sample. For example, homogeneity is achieved when the sampling error of the measurement is negligible or identical compared to the total error of the measurement. All other things being equal, (i) the greater the acoustic energy, the shorter the time required to achieve homogeneity, and vice versa, and (ii) the closer the frequency is to resonance with the polymer solid, the shorter the time required to achieve homogeneity, and vice versa.

[0021] A homogeneous mixture produced by the method can be characterized as homogeneous in that the liquid additive is adsorbed substantially uniformly as a film on the outer surface and any accessible inner surface of the polyolefin solid. "Adsorbed substantially uniformly" means that substantially all accessible surfaces of the polyolefin polymer solid have at least some liquid additive adsorbed thereon, although the amount of liquid additive adsorbed can vary across the surface. When adsorbed on the surface of the polyolefin solid, the liquid additive can remain thereon, or at least a portion can be immersed or absorbed or migrated into the polyolefin solid to create an impregnated polyolefin solid containing at least a portion of the liquid additive below the surface. In embodiments where some or all of the liquid additive is immersed or absorbed or migrated into the polyolefin solid, the surface of the polyolefin solid can appear to be semi-dry or dry (free of liquid additive), but the total weight of the liquid additive-impregnated polyolefin solid will be equal to the weight of the heterogeneous mixture from which the homogeneous mixture is made.

[0022] The method enables the production of a homogeneous mixture comprising a polyolefin solid and at least one liquid additive without using melt extrusion or melt compounding, which requires melting the polyolefin solid. Thus, the thermal history of the homogeneous mixture produced by the method is less detrimental (e.g., less oxidative degradation and / or less scorch or premature crosslinking) than the thermal history of a relatively homogeneous mixture produced by melt extrusion or melt compounding. For example, the homogeneous mixture produced by the method can have improved curing properties (e.g., lower hot creep %), improved mechanical properties (e.g., higher tensile strength, greater elongation at break) before and / or after its thermal aging.

[0023] Liquid means a substance in an amorphous state that is intermediate between a gas and a solid, has a stable volume, but does not have a defined shape.

[0024] Melting means changing a material from a solid state to a liquid state. Typically, melting means that the change is complete such that the liquid state of the material contains no unmelted solid form of the material. The temperature of the material characterized as solid or liquid is 20 °C.

[0025] Polyolefin means any polymer derived from polymerizing an olefin-functional monomer or copolymerizing at least two olefin-functional monomers, or a mixture of such polymers. A polyolefin can be amorphous (i.e., having a glass transition temperature but no melting point in differential scanning calorimetry (DSC)) or semi-crystalline (i.e., having a glass transition temperature and a melting point in DSC).

[0026] Examples of suitable polyolefins include ethylene-based polymers such as polyethylene homopolymers and ethylene-based copolymers, propylene-based polymers such as polypropylene homopolymers and propylene-based copolymers, halogenated polyolefins, grafted alkenyl-functional monocyclic organosiloxane-polyethylene copolymers, ethylene / alkenyl-functional monocyclic organosiloxane copolymers, and polystyrene polymers such as those described in US2012 / 0209056A1. Examples of halogenated polyolefins include poly(vinyl chloride) polymers (PVC), chlorinated poly(vinyl chloride) polymers (CPVC), chlorinated polyethylene polymers, chlorinated natural or synthetic rubbers, chlorinated polystyrene, poly(vinyl bromide) polymers, brominated butadiene / styrene copolymers, brominated polystyrene polymers, brominated natural or synthetic rubbers, and copolymers of vinyl chloride and copolymerizable ethylenically unsaturated monomers. Examples of copolymerizable ethylenically unsaturated monomers include vinyl acetate, vinyl butyrate, vinyl benzoate, vinylidene chloride, alkyl fumarates, alkyl maleates, vinyl propionate, alkyl acrylates, alkyl methacrylates, methyl alpha-chloroacrylate, styrene, trichloroethylene, vinyl ether, vinyl ketone, 1-fluoro-2-chloroethylene, acrylonitrile, chloroacrylonitrile, allylidene diacetate, and chloroallylidene diacetate, and any mixture of two or more thereof. For details, see US10,119,015B2. The polyolefin can be a thermoplastic elastomer or a compatibilizer, such as those described in US8,697,787B2. The polyolefin that is a copolymer can be a bipolymer (produced by polymerizing two different olefin monomers), a terpolymer (produced by polymerizing three different olefin monomers), or a tetrapolymer (produced by polymerizing four different olefin monomers). The polyolefin that is a copolymer can be a block copolymer or a random copolymer.

[0027] In some embodiments, the polyolefin is an ethylene-based polymer. Examples of suitable ethylene-based polymers are polyethylene homopolymers, ethylene / (C4-C 20 ) alpha-olefin copolymers, ethylene / propylene copolymers, ethylene / propylene / diene monomer (EPDM) copolymers, such as ethylene / propylene / 1,3-butadiene terpolymers, and ethylene / 1-butene / styrene copolymers. Examples of suitable ethylene / (C4-C 20 ) alpha-olefin copolymers are ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, and ethylene / 1-octene copolymers. The ethylene-based polymer can be ultra-low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), or ultra-high-density polyethylene (UHDPE). Many of the ethylene-based polymers are sold under trade names such as AFFINITY, ATTANE, DOWLEX, ENGAGE, FLEXOMER, or INFUSE by The Dow Chemical Company. Other ethylene-based polymers are sold under trade names such as TAFMER, EXCEED, and EXACT by other suppliers.

[0028] A monomer-based polymer such as an "ethylene-based polymer" or a "propylene-based polymer" means a polymer that includes structural units derived from 51 to 100 weight percent (wt%) of a monomer (e.g., ethylene or propylene) and structural units derived from one or more comonomers different from the monomer in an amount of 0 to 49 wt%.

[0029] An olefin-functional monomer means an organic molecule containing at least one polymerizable carbon-carbon double bond, and the organic molecule is composed of carbon atoms, hydrogen atoms, optionally at least one halogen atom, and optionally at least one heteroatom selected from N, O, S, Si, or P. Typically, at least one heteroatom includes an oxygen atom and / or a silicon atom. Examples of olefin-functional monomers are ethylene, propylene, (C4-C 20 ) alpha-olefins, 1,3-butadiene, norbornene, 5-ethylidene-2-norbornene, vinyl fluoride, vinyl chloride, vinyl bromide, vinyl iodide, vinyl acetate, (C1-C6) alkyl acrylate, (C1-C6) alkyl methacrylate, vinyltrialkoxysilanes such as vinyltrimethoxysilane of the formula H2C=C(H)Si(OCH3)3, or alkenyl-functional monocyclic organosiloxanes such as 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, “(D Vi )3” (CAS No. 3901-77-7) or 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-cyclotetrasiloxane, “(D Vi )4” (CAS No. 2554-06-5).

[0030] Solid means the state of a substance having a stable volume and a defined shape. It can be amorphous, crystalline, or semi-crystalline.

[0031] Solidification means changing a material from a liquid-state substance to a solid-state substance. Typically, solidification means that the change is complete such that the solid-state substance does not contain the uncured form of the material.

[0032] Applying acoustic energy at a frequency of 20 to 100 Hz, without being restricted by theory, is thought to generate sound waves that rapidly vibrate the polyolefin solid. They experience a relatively large physical displacement, and this magnitude and speed are thought to be a function of the frequency and acoustic intensity. This vibration of the polyolefin solid results in their rapid mixing with at least one liquid additive to form a first homogeneous mixture. The first homogeneous mixture is thus produced without solidifying at least one liquid additive, optionally without mechanical mixing of the polyolefin solid and at least one liquid additive, and without solidifying at least one liquid additive or melting the polyolefin solid. This method is different from previous mixing methods that rely on mechanical blending of liquid additives with polyolefin solids (e.g., in a stirred tank apparatus) or melts (e.g., in a twin-screw extruder apparatus).

[0033] Sounds with a frequency less than 20 Hertz (Hz) are called "ultra-low frequency sounds", 20 Hz to 20 kilohertz (kHz) are called "acoustic", and above 20 kHz (up to a maximum of 200 megahertz (MHz) or more) are called "ultrasonic". Without being restricted by theory, ultra-low frequency sounds and ultrasonic waves, as well as acoustic sounds above 100 Hz, are not thought to be able to rapidly vibrate the polyolefin solid in a heterogeneous mixture in such a way as to produce its relatively large physical displacement and thereby result in a homogeneous mixture. In this specification, applying acoustic energy at a frequency of 20 to 100 Hz is called "acoustic mixing".

[0034] The method may further include a feature that does not include mechanically moving the polyolefin solid or heterogeneous mixture during the application step. Mechanical movement means initiation by applying a direct contact force through which a physical object (e.g., a stirrer paddle, screw, plunger, or blender) comes into contact and thereby moves the material, either manually or via a machine. Examples of mechanical movement are stirring, screw mixing, plunger mixing, blender mixing, and other direct physical contacts. The contact force does not include electromagnetic force, gravitational force, acoustic force, and convective force.

[0035] The method may further include a feature that substantially or completely does not include immersing (or absorbing) a liquid additive into the polyolefin solid during the application step. Immersion requires the miscibility of the liquid additive in the polyolefin solid and effective immersion conditions. Such immersion conditions include a sufficient time (e.g., 8 to 16 hours) and a sufficient temperature from ambient temperature (e.g., 20 °C) to high temperature (e.g., 60 to 90 °C) to enable the movement of the liquid additive into the polyolefin solid.

[0036] The expression "heterogeneous mixture" may, in some cases, refer to a numbered embodiment or the first or second heterogeneous mixture of the claims, or a heterogeneous mixture of an unnumbered embodiment.

[0037] Heterogeneous mixtures. Neat polyolefin solids without liquid additives can be produced by contacting them with liquid additives without homogenizing them. Alternatively, homogeneous mixtures produced by acoustic mixing or comparative melt mixing of the present invention can be produced by contacting them with a second liquid additive and / or particulate solid additive without homogenizing them. Alternatively, by heterogenizing a homogeneous mixture of a polyolefin solid and a liquid additive, for example, allowing the homogeneous mixture to stand at 25 °C for a time sufficient to cause some aggregation of the liquid additive in the polyolefin solid or migration of the liquid additive to the surface of the polyolefin solid, it can be produced. Alternatively, it can be produced by heating a heterogeneous mixture of a polyolefin solid and a low-melting-point solid additive having a melting temperature lower than the melting temperature of the polyolefin solid, the heating being for a time sufficient to melt at least some or all of the low-melting-point solid additive to a temperature higher than the melting temperature of the low-melting-point additive and lower than the melting temperature of the polyolefin solid.

[0038] Heterogeneous mixtures may not have been homogenized previously or may be heterogenized as described above. In either case, a heterogeneous mixture is a non-uniform physical combination of substances, for example, consisting of unblended or partially (incompletely) blended components. Homogenization of a heterogenized mixture can reconstitute the homogeneous mixture of its precursor without remelting the polyolefin.

[0039] Polyolefin solid. A fine solid-state substance (i.e., solid particles) in the form of a polymer macromolecule independently containing at least 5, or 10 to 200,000 constitutional units derived from polymerizing one or more olefin-functional monomers. Examples of olefin-functional monomers are ethylene, alpha-olefins, dienes, unsaturated carboxylic acid esters, and olefin-functional hydrolyzable silanes. The polyolefin of the polyolefin solid can be an ethylene-based polymer containing 51 to 100% by weight of ethylene units derived from polymerizing ethylene, and 49 to 0% by weight of one or two olefin-functional monomers (comonomers) selected from propylene; (C4-C8) alpha-olefins such as 1-butene, 1-hexene, or 1-octene; unsaturated carboxylic acid esters, and olefin-functional hydrolyzable silanes, i.e., comonomer units derived from polymerizing the comonomers. Alternatively, the polyolefin of the polyolefin solid can be a propylene-based polymer containing 51 to 100% by weight of propylene units derived from polymerizing propylene, and 49 to 0% by weight of one or two olefin-functional monomers (comonomers) selected from ethylene; (C4-C8) alpha-olefins such as 1-butene, 1-hexene, or 1-octene; unsaturated carboxylic acid esters, and olefin-functional hydrolyzable silanes, i.e., comonomer units derived from polymerizing the comonomers. Examples of alpha-olefins are (C4-C8) alpha-olefins such as propylene, 1-butene, 1-hexene, or 1-octene, and (C 10 -C 20) It is an alpha-olefin. Examples of dienes are 1,3-butadiene. Examples of unsaturated carboxylic acid esters are alkyl acrylates, alkyl methacrylates, and vinyl carboxylates (e.g., vinyl acetate). Examples of olefin-functional hydrolyzable silanes are vinyltrialkoxysilane, vinyltris(dialkylamino)silane, and vinyl(trioximo)silane. Examples of polyolefins of polyolefin solids are polyethylene homopolymers, polypropylene homopolymers, ethylene / propylene copolymers, ethylene / (C4-C8) alpha-olefin copolymers, ethylene / propylene / 1,3-butadiene copolymers, ethylene / unsaturated carboxylic acid ester copolymers, and ethylene / vinyl-functional hydrolyzable silane copolymers.

[0040] The polyolefin polymer solid can be porous or non-porous. The polyolefin polymer solid can include powders, granules, or pellets.

[0041] Liquid additives. A neat liquid or a solution of a liquid or solid additive (solute) dissolved in a liquid solvent. The neat liquid is not a polyolefin polymer macromolecule and is composed of molecules having temperature characteristics (i) or (ii): (i) a freezing point below 0 °C, or between 0 and 20.0 °C, or (ii) a melting point between 20.1 and 99 °C, or between 30.0 and 79.9 °C, or between 40.0 and 69.9 °C. The liquid additive solute in the solution can be the same compound described for the neat liquid. The solid additive solute in the solution can be a compound having a solubility of at least 1 wt% in the liquid solvent. The liquid solvent can be an organic liquid selected to have a boiling point above the temperature of the heterogeneous mixture during the application step. Suitable liquid solvents are hydrocarbons (e.g., mineral oil or xylene), ethers (e.g., dibutyl ether), and blends of two or more of them. In some embodiments, the liquid additive is added to the polyolefin solid as a neat liquid and the heterogeneous mixture does not contain any liquid solvent.

[0042] The term "liquid additive" is used to describe the state of matter of the additive at the temperature of the heterogeneous mixture during the step of applying acoustic energy, and when the temperature of the heterogeneous mixture during the applying step is higher than the ambient temperature, it is not necessarily required that the additive be liquid at the ambient temperature (e.g., 23°C). In some embodiments, the liquid additive is liquid at the ambient temperature (e.g., 23°C).

[0043] The liquid additive may or may not impart at least one beneficial functional property to the homogeneous mixture and / or its polyolefin solid. For example, the liquid additive may simply be a filler material used only to reduce the cost of the product made from the homogeneous mixture as compared to the cost of the product made from the polyolefin solid without the liquid additive and without providing it with a functional benefit. Alternatively, the liquid additive may impart at least one functional property to the homogeneous mixture and / or its polyolefin solid, such as color, increased stability (e.g., against degradation, embrittlement, sagging, or dielectric loss effects from exposure to heat, ultraviolet light, electricity, and / or water), a crosslinking source (if the liquid additive is a crosslinking aid or catalyst for enhancing the crosslinking of the polyolefin), increased conductivity (e.g., electrical and / or thermal conductivity), and increased modulus of elasticity.

[0044] Each heterogeneous mixture and homogeneous mixture may independently contain only one liquid additive or a combination of two or more different liquid additives.

[0045] The heterogeneous mixture, and thus the homogeneous mixture made therefrom by the method, may not include (i.e., may be lacking) particulate solid additives. In these embodiments, the heterogeneous mixture, and thus the homogeneous mixture made therefrom by the method, may consist essentially of or consist of a polyolefin solid and at least one liquid additive.

[0046] Alternatively, the heterogeneous mixture and thus the homogeneous mixture produced therefrom may further comprise particulate solid additives that are different from the polyolefin solids. In these embodiments, the heterogeneous mixture and thus the homogeneous mixture produced therefrom may consist essentially of, or consist of, polyolefin solids, at least one such liquid additive, and at least one such particulate solid additive.

[0047] Any particulate solid additive. A substance that is not, or does not contain, a polyolefin polymer, i.e., is not a polymer of any type or a polymer whose constituent units are not derived from olefinically functional monomers. The particulate solid additive, if present, may be characterized by a glass transition temperature and / or a melting temperature higher than the melting temperature of the polyolefin solid, e.g., higher than 140 °C or higher than 180 °C. The actual glass transition temperature and melting temperature of the particulate solid additive, if present, are high enough that they are not critical as long as the particulate solid additive does not glass transition or melt during the application step. The heterogeneous and homogeneous mixtures may include zero particulate solid additives, or one particulate solid additive, or a combination of two or more different particulate solid additives. The particulate solid additive can be inorganic or organic. Examples include carbon black, carbon nanotubes, diamond powder, graphite, graphene, powdered metals, powdered metal oxides, solid flame retardants, silica, alumina, and silicate glass beads. In some embodiments, the heterogeneous mixture, the production method, and the homogeneous mixture produced thereby do not include particulate solid additives.

[0048] The polyolefin of the polyolefin solid can be (A) an HSG-FP copolymer. The (A) HSG-FP copolymer is prepared by copolymerizing monomers including ethylene and optionally an olefin-functional comonomer, and at least one olefin-functional comonomer is an olefin-functional hydrolyzable silane. The composition of the (A) HSG-FP copolymer can be characterized by constitutional units selected from ethylene units, alkylene hydrolyzable silyl group units, optionally propylene units, and optionally comonomer units derived from any olefin comonomer. Optionally, 0, 1, or more olefin comonomers can be selected from (C4-C 20 ) alpha-olefins, olefinically unsaturated carboxylic acids, olefinically unsaturated carboxylic acid esters, olefinically unsaturated carboxylic acid anhydrides, and combinations thereof. The carboxylic acid can be a monocarboxylic acid or a dicarboxylic acid. The carboxylic acid ester can be a monocarboxylic acid ester, a dicarboxylic acid monoester, or a dicarboxylic acid diester. The olefinically unsaturated carboxylic acid can be a terminal unsaturated (C2-C8) carboxylic acid, or (meth)acrylic acid, or an unsaturated dicarboxylic acid. The olefinically unsaturated carboxylic acid ester can be a (C2-C8) carboxylic acid vinyl ester, or a (C2-C5) carboxylic acid vinyl ester (e.g., vinyl acetate, vinyl propionate, or vinyl butyrate), or a (meth)acrylic acid (C1-C8) alkyl ester, or a (meth)acrylic acid (C1-C3) alkyl ester, or a di(C1-C8) alkyl diester of an unsaturated dicarboxylic acid, or a mono(C1-C8) alkyl ester of an unsaturated dicarboxylic acid, or a mono(C1-C8) alkyl ester of maleic acid. (Meth)acrylate means H2C=CHCO2- or H2C=C(CH3)CO2-. The CTA can be acetone, methyl ethyl ketone, propionaldehyde, 2-propanol, ethyl acetate, isobutene, butane, 2-methylpropane, ISOPARTM-C, ISOPARTM-E, ISOPARTM-H, or any combination of two or more thereof. The CTA, when present, can be 0.03 to 10% by weight of the polymerization reaction mixture.

[0049] (A) The HSG-FP copolymer can be characterized by a total hydrolyzable silyl group content of 0.43 to 0.99 mol%. The total mol% of the hydrolyzable silyl group content is calculated from the weight% value of the hydrolyzable silyl group content, and the weight% value is determined according to the fluorescent X-ray (XRF) test method described below. For example, when at least one alkenyl-functional hydrolyzable silane is vinyltrimethoxysilane (VTMS), its molecular weight is 148.23 g / mol, and when the comonomer content is 2.0 wt%, mol% = 0.38 mol%. When the VTMS comonomer content is 5.0 wt%, mol% = 0.99 mol%. The mol% hydrolyzable silyl group content at any given weight% hydrolyzable silyl group content value varies inversely with the molecular weight of at least one alkenyl-functional hydrolyzable silane from which the hydrolyzable silyl group is derived.

[0050] (A) The HSG-FP copolymer contains hydrolyzable silyl groups. These groups are independently monovalent groups of the formula (R 2 ) m (R 3 ) 3-m Si—, where the subscript m is an integer of 1, 2, or 3, and each R 2 is independently H, HO—, (C1-C8) alkoxy, (C2-C6) carboxy, phenoxy, (C1-C6) alkyl-phenoxy, (C1-C6) alkyl(H)N—, ((C1-C6) alkyl)2N—, (C1-C6) alkyl(H)C═NO—, or ((C1-C6) alkyl)2C═NO—, and each R 3 is independently (C1-C8) alkyl or phenyl. Each R 2 may not contain H and HO—, or may not contain phenoxy and (C1-C6) alkyl-phenoxy. Each R 2is independently (C1-C6)alkoxy, (C2-C6)carboxy, ((C1-C6)alkyl)2N-, (C1-C6)alkyl(H)C=NO-, or ((C1-C6)alkyl)2C=NO-, or can be (C1-C6)alkoxy, or (C2-C6)carboxy, or ((C1-C6)alkyl)2N-, or (C1-C6)alkyl(H)C=NO-, or ((C1-C6)alkyl)2C=NO-. All hydrolyzable silyl groups of the (A) HSG-FP copolymer can be the same. The hydrolyzable silyl group is derived from the hydrolyzable silyl group of at least one alkenyl-functional hydrolyzable silane (comonomer), from which the comonomer unit of the (A) HSG-FP copolymer containing such a group is produced.

[0051] Optional additive (B) silanol condensation catalyst. (B) can be selected from any one of (i)-(iv): (i) Bronsted acid, (ii) Bronsted base, (iii) Lewis acid, and (iv) Lewis base. (B) can be either (i) or (iii), or either (ii) or (iv). (B) can be a Lewis acid, which can be dialkyltin dicarboxylate. (B) can be a Bronsted acid, which can be a sulfonic acid of the formula RSO3H, wherein R is (C1-C 10 )alkyl, (C6-C 10 )aryl, (C1-C 10 )alkyl-substituted (C6-C 10 )aryl, or (C6-C 10 )aryl-substituted (C1-C 10 )alkyl, or a blocked sulfonic acid, which is produced in situ from a sulfonic acid.

[0052] Any additive (C) antioxidant: an organic molecule that inhibits oxidation, or an aggregate of such molecules. The (C) antioxidant has a different composition from the (F) stabilizer, which means that when a heterogeneous or homogeneous mixture contains both (C) and (F), the compound used as (C) is different from that used as (F). The (C) antioxidant functions to provide antioxidant properties to a heterogeneous or homogeneous mixture and / or a cured polymer product produced by curing a homogeneous mixture.Examples of suitable (C) are bis(4-(1-methyl-1-phenylethyl)phenyl)amine (e.g., NAUGARD 445), 2,2'-methylenebis(4-methyl-6-t-butylphenol) (e.g., VANOX MBPC), 2,2'-thiobis(2-t-butyl-5-methylphenol) (CAS No. 90-66-4, 4,4'-thiobis(2-t-butyl-5-methylphenol) (also known as 4,4'-thiobis(6-tert-butyl-m-cresol), CAS No. 96-69-5, commercially available LOWINOX TBM-6), 2,2'-thiobis(6-t-butyl-4-methylphenol) (CAS No. 90-66-4, commercially available LOWINOX TBP-6), tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6-trione (e.g., CYANOX 1790), pentaerythritol tetrakis(3-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)propionate) (e.g., IRGANOX 1010, CAS No. 6683-19-8), 2,2'-thiodiethanol ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid (e.g., IRGANOX 1035, CAS No. 41484-35-9), distearyl thiodipropionate ("DSTDP"), dilauryl thiodipropionate (e.g., IRGANOX PS 800), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (e.g., IRGANOX 1076), 2,4-bis(dodecylthiomethyl)-6-methylphenol (IRGANOX 1726), 4,6-bis(octylthiomethyl)-o-cresol (e.g., IRGANOX 1520), and 2',3-bis[[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl]]propionohydrazide (IRGANOX1024).(C) can be 4,4'-thiobis(2-t-butyl-5-methylphenol) (also known as 4,4'-thiobis(6-tert-butyl-m-cresol)), 2,2'-thiobis(6-t-butyl-4-methylphenol), tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6-trione, distearyl thiodipropionate, or dilauryl thiodipropionate, or any combination of two or more thereof. The combination may be tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6-trione and distearyl thiodipropionate. Heterogeneous and / or homogeneous mixtures may not contain (C). When present, the antioxidant (C) can be 0.01 to 1.5 wt%, or 0.1 to 1.0 wt% of the total weight of the heterogeneous and / or homogeneous mixture.

[0053] Any additive (D) is a colorant. For example, a pigment or a dye. For example, carbon black or titanium dioxide. Carbon black can be provided as a carbon black masterbatch which is a formulation of poly(1-butene-co-ethylene) copolymer (more than 95 wt% to less than 100 wt% of the total weight of the masterbatch), and carbon black (more than 0 wt% to 5 wt% or less of the total weight of the masterbatch). Carbon black is a microcrystalline form of quasi-crystalline carbon and has a high surface area to volume ratio, but lower than that of activated carbon. Examples of carbon black are furnace carbon black, acetylene carbon black, conductive carbon (e.g., carbon fiber, carbon nanotube, graphene, graphite, and expanded graphite platelets). Heterogeneous and / or homogeneous mixtures may not contain (D). When present, (D) can be 0.1 to 35 wt%, or 1 to 10 wt% of the heterogeneous and / or homogeneous mixture.

[0054] Any additive (E) is a scorch retarder. The (E) scorch retarder functions to inhibit the early moisture curing of the heterogeneous and / or homogeneous mixture embodiments, which would occur from early or long-term exposure of the mixture to ambient air or when the mixture is at ambient or elevated temperature (e.g., during subsequent melt extrusion). Examples of (E) are octyltriethoxysilane and octyltrimethoxysilane and vinyltrimethoxysilane. The heterogeneous and / or homogeneous mixture may be without (E). When present, (E) can be from 0.001 to 5.0 wt%, or from 0.01 to 3.0 wt%, or from 0.10 to 1.5 wt%, or from 0.15 to 1.0 wt% of the heterogeneous and / or homogeneous mixture.

[0055] Any additive (F) A stabilizer (UV stabilizer) for stabilizing heterogeneous and / or homogeneous mixtures against ultraviolet light. The (F) stabilizer has a different composition from the (C) antioxidant, which means that when the mixture contains both (C) and (F), the compound used as (C) is different from the compound used as (F). Examples include hindered amine light stabilizers (HALS), benzophenones, or benzotriazoles. The (F) UV stabilizer can be a molecule that binds to at least one sterically bulky organic group and contains a basic nitrogen atom that functions as an inhibitor of degradation or decomposition, or an aggregate of such molecules. HALS are compounds that have sterically hindered amino functional groups, inhibit oxidative degradation, and can also increase the shelf life of embodiments of mixtures containing organic peroxides. Examples of suitable (F) are dimethyl butanedioate, a polymer containing 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-ethanol (CAS number 65447-77-0, commercially available LOWILITE 62), and N,N'-bisformyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylenediamine (CAS number 124172-53-8, commercially available Uvinul 4050H). The heterogeneous and / or homogeneous mixture may not contain (F). When present, the (F) UV stabilizer can be from 0.001 to 1.5 wt%, or from 0.002 to 1.0 wt%, or from 0.05 to 0.1 wt% of the heterogeneous and / or homogeneous mixture.

[0056] Any additive (G) Processing aid: A molecule that reduces the adhesion of the polymer melt in manufacturing equipment such as extruders and dies and reduces the melt fracture of the material in embodiments where the homogeneous mixture is subsequently used therein. (G) can be a fluoropolymer, a polyorganosiloxane, a metal salt of a fatty carboxylic acid, a fatty carboxamide, a wax, an ethylene oxide (co)polymer, and a nonionic surfactant. The heterogeneous and / or homogeneous mixture may not contain (G). When present, the (G) processing aid can be from 0.05 to 5 wt% of the heterogeneous and / or homogeneous mixture.

[0057] Any additive (H) Flame retardant. The (H) flame retardant is a compound that inhibits or delays the spread of fire by suppressing chemical reactions in the flame. The (H) flame retardant can be (H1) minerals, (H2) organic halogen compounds, (H3) (organic) phosphorus compounds, (H4) halogenated silicones, (H5) any combination of two or more of (H1) to (H4), (H6) a combination of any one of (H1) to (H4) and a flame retardant synergist (e.g., antimony trioxide). Heterogeneous and / or homogeneous mixtures may not contain (H). When present, the (H) flame retardant can be 0.1 to 80.0 wt%, or 1 to 50.0 wt%, or 5 to 30.0 wt% of the heterogeneous and / or homogeneous mixture.

[0058] The heterogeneous and / or homogeneous mixture may further contain a polymer (I) or a styrene polymer (not (A)) that is not (A). The polymer (I) that is not (A) can be a polyolefin-based polymer having a composition different from that of the (A) polymer. The polymer (I) that is not (A) can be a polyolefin, a styrene polymer, a rubber, a poly(vinyl chloride) polymer, a polyorganosiloxane such as polydimethylsiloxane (PDMS), or a blend of any two or more thereof.

[0059] Manufactured article. A manufactured article made from a homogeneous mixture may include its molded form. Examples include substrates, tapes, films, laminate layers, foams, coatings on pipes.

[0060] Coated conductor. The manufactured article can be a coated conductor that includes a conductive core and a polymer layer that at least partially surrounds the conductive core, with at least a portion of the polymer layer including a homogeneous mixture or a cured polymer product that cures it. The entire polymer layer can include a cured polymer product. The conductive core can be in a linear shape (e.g., like a wire), having a length and proximal and distal ends spaced apart from each other by the length of the linear shape, and the polymer layer can surround the conductive core except at the proximal and distal ends. The coated conductor can further include one or more additional polymer layers, and / or an outer shield layer (e.g., a metal sheath or sleeve), which may or may not include a cured polymer product. The coated conductor can include one or two insulating layers, at least one of which is an insulating layer including a cured polymer product, and alternatively or additionally, one or two semiconductor layers, at least one of which includes a cured polymer product including carbon black, and alternatively or additionally, an outer shield layer including a cured polymer product.

[0061] (A) A moisture-curable embodiment of a homogeneous mixture containing an HSG-FP copolymer can be moisture-cured by exposure to ambient air or by immersion in hot water at 70 °C to 95 °C to produce a cured polymer product. The degree of cross-linking of the cured polymer product can be characterized by measuring the percent hot creep.

[0062] Substitution: Any one, all except one, or each functional group can be unsubstituted.

[0063] Or, it precedes different embodiments. "May" is not essential and confers permission for selection. "Optional" (optionally): Absence (or exclusion), or presence (or inclusion).

Examples

[0064] Melt Index ("I2"): Formerly known as "Condition E", measured according to ASTM D1238-13 using conditions of 190 °C / 2.16 kg, in units of grams per 10 minutes (g / 10 min).

[0065] Using XRF spectrometry, determine the weight percent (wt%) of silicon atoms (Si) in a test sample of the (A) HSG-FP copolymer, and then calculate the hydrolyzable silane comonomer unit wt%. Using a Buehler SimpliMet 300 automatic mounting press preheated at 115.6 °C (240 °F) for 3 minutes, press a test sample in powder form at 8.3 megapascals (MPa, 1,200 pounds per square inch (psi)) for 1 minute to form a plaque having a thickness of about 6 mm, and cool the plaque to 25 °C. Use a wavelength dispersive X-ray fluorescence spectrometer from PANalytical Axios to analyze the Si atomic content of the plaque by wavelength dispersive XRF. Determine the Si atomic content by comparing the line intensity of the XRF spectrum with a calibration curve of Si atomic content established using a polymer standard of known Si atomic concentration measured individually using neutron activation analysis (NAA) or inductively coupled plasma (ICP) methods. Using the wt% value of Si atoms measured by XRF and the molecular weight of at least one alkenyl-functional hydrolyzable silane comonomer from which the hydrolyzable silyl group is derived, calculate the hydrolyzable silyl group comonomer unit wt% (i.e., the weight % of the hydrolyzable silyl group) in the (A) HSG-FP copolymer. For the hydrolyzable silyl group derived from vinyltrimethoxysilane (VTMS), use a VTMS molecular weight of 148.23 g / mol. To calculate the hydrolyzable silyl group content of the (A) HSG-FP copolymer (in wt% of hydrolyzable silyl group comonomer units), use the Si atomic wt% ("C") obtained by XRF and the following formula: p = C*(m / 28.086)(1 / 10000 ppmw), where * means multiplication, / means division, p is the weight % of the hydrolyzable silyl group in (A), C is the Si atomic amount (XFR) in parts per million by weight (ppmw), m is the molecular weight in g / mol of at least one alkenyl-functional hydrolyzable silane comonomer from which the hydrolyzable silyl group is derived, 28.086 is the atomic weight of a silicon atom, and 10000 ppmw is the number of parts per million by weight in 1.00 wt%.For example, if XRF indicates 379 ppmw of Si atoms in the (A) HSG-FP copolymer and the comonomer used to make (A) is VTMS having a molecular weight of 148.23 g / mol, the weight % of the comonomer content is 0.20 wt%. To calculate the mol% of the hydrolyzable silyl group comonomer units in the (A) HSG-FP copolymer of at least one alkenyl-functional hydrolyzable silane comonomer used, use the calculated weight % of the hydrolyzable silyl group comonomer units in (A) and the following formula: G = 100*(p / m) / [(p / m)+(100.00 wt% - p) / 28.05 g / mol], where * means multiplication, G is the mole percent (mol%) of the hydrolyzable silyl groups in (A), p is the weight % of the hydrolyzable silyl groups in (A), m is the molecular weight in g / mol of at least one alkenyl-functional hydrolyzable silane comonomer from which the hydrolyzable silyl group is derived, and 28.05 g / mol is the molecular weight of monomer ethylene (H2C=CH2). For example, when the comonomer content is 2.0 wt% and the comonomer is VTMS, p = 2.0 wt%, m = 148.23 g / mol, and G = 0.38 mol%. When the comonomer content is 5.0 wt% and the comonomer is VTMS, p = 5.0 wt%, m = 148.23 g / mol, and G = 0.99 mol%. When making (A) using two or more alkenyl-functional hydrolyzable silane comonomers with different molecular weights, the molecular weight used in the calculation of the total mol% of all hydrolyzable silyl groups in (A) is the weighted average molecular weight of the comonomers. The weighting can be determined by the ratio of the amounts of comonomers fed to the GPP reactor, or by NMR spectroscopy of the (A) HSG-FP copolymer, when each hydrolyzable silyl group is bonded to a different type of carbon atom (e.g., tertiary vs. secondary carbon atoms), or by Fourier transform infrared (FT-IR) spectroscopy calibrated to provide the quantification of the various types of comonomers, to determine the relative amounts of the different comonomer units of the (A) HSG-FP copolymer.

[0066] Tape Preparation Method: For ambient curing and hot creep test evaluation, it is used to prepare a moisture-curable polyethylene formulation in tape form. The formulation prepared according to the above method is fed into a Brabender 1.905 cm (3 / 4 inch) extruder equipped with a 25:1 double mixing zone (pineapple) screw, a 40 / 60 / 40 mesh screen pack, and a 5.08 cm (2 inch) wide head die. The extruder has a temperature profile over four zones of 150 °C, 160 °C, 170 °C, and 170 °C at the head die, and the screw speed is 60 revolutions per minute (rpm). Thereby, different formulations are made in the form of tapes having an average thickness of 1.37 - 1.70 mm (54 - 67 mils).

[0067] Ambient Moisture Curing Method. For property evaluation and comparison, the ambient curing conditions were controlled as follows. The tape test pieces made by the tape preparation method were cured for up to 182 days in an environment of 23 °C ± 2 °C and 50% ± 2% RH as shown in Tables 3 - 5 below to produce cured polymer products. The hot creep of the cured polymer products was measured according to the hot creep test method.

[0068] Hot Water Curing Method. The tape test pieces made by the tape preparation method were immersed in a water bath at 90 °C ± 2 °C for 20 hours as shown in Tables 3 - 5 below to produce cured polymer products. The hot creep of the cured polymer products was measured according to the hot creep test method.

[0069] Hot Creep Test Method. In a test sample of a cured polymer product prepared by a moisture curing method, the degree of crosslinking, and thus the degree of curing, is measured. The test sample is subjected to a hot creep test method at a load, weight, and 200 °C in accordance with UL 2556, Wire and Cable Test Methods, Section 7.9. Load weight = CA * 200 kilopascals (kPa, 29.0 pounds / feet per square inch). CA is the cross-sectional area of a dogbone-shaped sample cut from a pressed plaque prepared according to the plaque preparation method. Three dogbone-shaped test specimens are prepared for each test material. Mark the test specimens with two marks at the original distance G from each other, where G = 25 + / - 2 mm. Place in the upper grip of the hot creep test assembly. Apply a hanging load of 0.2 megapascals (MPa) from the gripped test specimen. Heat the test assembly containing the dogbone-shaped test specimen in a preheated circulating air oven at 200 °C + / - 2 °C for 15 minutes, and then, with the load still attached, measure the final length D e between the marks on the test specimen. Calculate the hot creep elongation percentage (HCE) according to Equation 1: HCE = [100 * (D e - G)] / G (1). Divide the amount of elongation by the initial length to obtain the hot creep measurement as a percentage. The lower the hot creep percentage, the lower the degree of elongation of the test sample under load, and thus the greater the degree of crosslinking, and thus the greater the degree of curing. A lower hot creep value suggests a higher degree of crosslinking. The hot creep measurement of a sample cured by immersion in a water bath at 90 °C ± 2 °C for 20 hours indicates the final degree of crosslinking of the cured product. The higher the final degree of crosslinking of the cured polymer product, the more non-crosslinkable polymer or non-moisture curable (e.g., peroxide and / or photo-curable only) polymer (e.g., other than HSG-FP copolymer (e.g., polyethylene)) can be incorporated into the moisture curable polyethylene formulation while still achieving satisfactory hot creep performance of 175% or less after curing.

[0070] Wire Coating Preparation Method: A variable speed drive, 25:1 Maddock mixing head screw, BRABENDER cross-head wire die, laboratory water-cooled trough with air wipe, laser micrometer, and variable speed wire puller were used, with temperature profiles of 150 °C (zone 1), 170 °C (zone 2), 190 °C (zone 3), and 195 °C, (head / die), and a BRABENDER 3 / 4 inch (1.91 cm) extruder equipped with a 40 / 40 mesh screen pack. The melt was extruded at a screw speed of 40 revolutions per minute (rpm) and a take-up speed of approximately 2.4 meters per minute (m) (8 feet), and the coating of the molten mixture was deposited onto a 14 AWG solid copper wire (diameter 1.628 mm, AMG is the American wire gauge). The coating had a nominal wall thickness of 0.8 mm.

[0071] Coated Wire Curing Method: Wire samples prepared according to the wire coating preparation method were then cured by immersing them in a water bath maintained at 95 °C for different times, as reported hereafter, to obtain cured insulated wire samples. By slightly pulling down the copper to facilitate the removal of the insulator, a portion of the subsequently cured coating ("insulator") was peeled off and its hot creep performance was measured. Insulated samples without conductors were tested for hot creep in an oven set at 200 °C under a stress of 0.2 MPa at the bottom of the sample where the sample was stretched for 15 minutes. The results are reported as the average elongation of three samples expressed as a percentage. See the hot creep test method for details.

[0072] Moving Die Rheometer (MDR) Test Method (MDR: ML (N-m) at 182°C, MDR: MH-ML (N-m) at 182°C): ASTM D5289-12, Standard Test Method for Rubber Property - Vulcanization Using Rotorless Curemeters. The torque of a 6-gram cold press test sample is measured using the following procedure. While monitoring the change in torque, the test sample, directly obtained from a Brabender mixing bowl, is heated at 182°C for 20 minutes with a 0.5-degree arc oscillation in a Moving Die Rheometer (MDR) instrument MDR2000 (Alpha Technologies). Designate the measured minimum torque value as "ML" expressed in decinewton meters (dN-m). As curing or crosslinking progresses, the measured torque value increases and ultimately reaches the maximum torque value. Designate the maximum or highest measured torque value as "MH" expressed in dN-m. All other things being equal, the greater the MH torque value, the greater the degree of crosslinking. All other things being equal, the greater the MH-ML torque value difference, the greater the amount of crosslinking. Measured in pound-inches (lb.-in.), converted to newton-meters (N-m), where 1.00 lb.-in. = 0.113 N-m.

[0073] Polyolefin Solid 1: Linear low-density polyethylene (LLDPE) with a density of 0.92 g / cm 3 and a melt index (I2) of 0.65 g / 10 minutes. Used in pellet form.

[0074] Polyolefin Solid 2: A reactor HSG-FP copolymer produced by copolymerizing ethylene and vinyltrimethoxysilane (VTMS) at high pressure and temperature in the presence of an organic peroxide catalyst and in the absence of a metal-based catalyst. The HSG-FP copolymer had a trimethoxysilylethyl group content of 1.5 wt%, a density of 0.92 g / cm 3 and a melt index (I2) of 1.5 g / 10 minutes. Used in the form of dry pellets.

[0075] Polyolefin solid 3: A reactor HSG-FP copolymer produced by copolymerizing ethylene and 3-methacryloxypropyltrimethoxysilane (M3M) at high pressure and temperature in the presence of an organic peroxide catalyst and in the absence of a metal-based catalyst. Polyolefin solid 3 has a melt index (I2) of 0.9 g / 10 min and an M3M content of 0.9 wt%. It is used in the form of dry pellets.

[0076] Liquid additive 1: Vinyltrimethoxysilane (VTMS), an alkenyl-functional hydrolyzable silane comonomer, delivered as a neat liquid.

[0077] Liquid additive 2: Dicumyl peroxide (DCP), an organic peroxide, delivered as a neat liquid.

[0078] Liquid additive 3: Dibutyltin dilaurate (DBTDL), a moisture-curing catalyst, delivered as a neat liquid.

[0079] Liquid additive 4: Octyltriethoxysilane (OTES), a scorch retarder, delivered as a neat liquid. Available as PROSIL 9202.

[0080] Particulate solid additive 1: A natural (without colorant) catalyst masterbatch containing 85 wt% linear low-density polyethylene (LLDPE) with a density of 0.92 g / cm 3 and a melt index (I2) of 0.65 g / 10 min, 9 wt% low-density polyethylene (LDPE) with a density of 0.92 g / cm 3 and a melt index (I2) of 2 g / 10 min, 3.4 wt% of the solid antioxidant pentaerythritol tetrakis(3-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)propionate), and 2.6 wt% dibutyltin dilaurate. (Dry under vacuum at 60 °C overnight before use.)

[0081] Particulate solid additive 2: Alumina trihydrate (ATH), an in-situ moisture generator, delivered as a neat solid.

[0082] Comparative Example 1 (CE1): A homogeneous mixture was prepared by melt-mixing its components (Polyolefin solid 1 and Liquid additives 1 and 2 and Particulate solid additive 1) in an extruder. Polyolefin solid 1 was preheated in a glass bottle at 70 °C for 1 hour. Liquid additives 1 and 2 were added. It was tumble-mixed for 10 minutes. The glass bottle with the mixture was left in an oven at room temperature for 16 - 20 hours overnight to complete the immersion of Liquid additives 1 and 2 into Polyolefin solid 1. The obtained Polyolefin solid 1 immersed in Liquid additives 1 and 2 was physically blended with Particulate solid additive 1 to obtain a heterogeneous mixture. The Polyolefin solid 1 and Particulate solid additive 1 of the heterogeneous mixture were melted, and the heterogeneous mixture melt was mixed in a BRABENDER 3 / 4 inch (1.91 cm) extruder equipped with a variable speed drive, a 25:1 Maddock mixing head screw, a BRABENDER cross-head wire die, a laboratory water-cooled trough with an air wipe, a laser micrometer, and a variable speed wire puller, at temperature profiles of 150 °C (zone 1), 170 °C (zone 2), 190 °C (zone 3), and 195 °C, (head / die), and a 40 / 40 mesh screen pack to obtain a melt of Polyolefin solid 1, a melt of Particulate solid additive 1, and a homogeneously melt-mixed mixture of Liquid additives 1 - 3.

[0083] Comparative Example 1A (CE1A): The melt-mixed homogeneous mixture of CE1 was extruded as a coating onto a 14 AWG solid copper wire to mimic the production of a coated conductor, and the hot creep performance of the coating was measured. Using the same extruder and extruder conditions as CE1, the melt-mixed homogeneous mixture was extruded as a coating onto the wire according to the above wire coating preparation method. According to the coated wire curing method, the coating was cured to obtain the insulated wire of CE1A, a portion of the insulator was peeled off therefrom, and its hot creep performance was measured.

[0084] Inventive Example 1 (IE1): A homogeneous mixture is prepared by acoustically mixing its constituent components (polyolefin solid 1, and liquid additives 1 and 2, and particulate solid additive 1) in an acoustic mixer. 150 grams (g) of polyolefin solid 1, 2.41 g of liquid additive 1, and 0.16 g of liquid additive 2 are added to a glass bottle, and the contents of the bottle are acoustically mixed at 23 - 26 °C for 2 minutes using a RESODYN Acoustic Mixer (LabRAM Mixer) to produce a first homogeneous mixture. Then, 8 g of particulate solid additive 1 is added to form a second heterogeneous mixture. The second heterogeneous mixture is acoustically mixed for 0.5 minutes to obtain a second homogeneous mixture.

[0085] Inventive Example 1A (IE1A): The acoustically mixed second homogeneous mixture of IE1 is extruded as a coating onto a 14 AWG solid copper wire to mimic the production of a coated conductor, and the hot creep performance of the coating is measured. The second homogeneous mixture of IE1 is added to a BRABENDER 3 / 4 inch (1.91 cm) extruder, and polyolefin solid 1 and particulate solid additive 1 are melted to obtain the second homogeneous mixture as a melt. Using the same extruder and extruder conditions as in CE1, the melt is extruded as a coating onto the wire according to the above wire coating preparation method. The coating is cured according to the coated wire curing method to obtain an insulated wire of IE1A, a portion of the insulator is peeled off therefrom, and its hot creep performance is measured.

Table 1

[0086] In Table 1, the hot creep measurements carried out after curing a mixture of CE1 and IE1 to obtain the insulating wires of CE1A and IE1A surprisingly showed that the percentage elongation of the cured samples prepared by curing the acoustically mixed homogeneous mixture of the present invention for 0.5, 1, or 2 hours was beneficially lower than that of the cured samples prepared by curing the comparative melt-mixed homogeneous mixture for 0.5, 1, or 2 hours. That is, a greater degree of curing (crosslinking) is more rapidly and advantageously achieved with the mixture of the present invention. However, the percentage elongation of the cured samples prepared by curing the acoustically mixed homogeneous mixture of the present invention for 6 hours was higher than that of the cured samples prepared by curing the comparative melt-mixed homogeneous mixture for 6 hours. The main value of the present invention is easier mixing, which is illustrated by the foregoing.

[0087] Also, both the tensile strength before and after aging was higher for the acoustically mixed homogeneous mixture IE1 of the present invention than for the melt-mixed homogeneous mixture CE1.

[0088] Comparative Example 2 (CE2): A homogeneous mixture was prepared by melt-mixing its components (polyolefin solid 2 and liquid additive 4) by immersion. The polyolefin solid 2 was preheated in a glass bottle at 70 °C for 30 minutes. The liquid additive 4 was added. It was tumble-mixed for 10 minutes. The glass bottle containing the mixture was left in an oven at room temperature for 16 - 20 hours overnight to complete the immersion of the liquid additive 4 into the polyolefin solid 2.

[0089] Example of Invention 2 (IE2): In an acoustic mixer, a homogeneous mixture is prepared by acoustically mixing a polyolefin solid 2, a liquid additive 3, and a particulate solid additive 2. 160 g of the polyolefin solid 2 and the liquid additive 3 are added to a glass bottle to prepare a first heterogeneous mixture containing the polyolefin solid 2 and the liquid additive 3. Using a RESODYN Acoustic Mixer (LabRAM Mixer), the contents of the bottle are acoustically mixed at 23 - 26 °C for 2 minutes to prepare a first homogeneous mixture containing the polyolefin solid 2 and the liquid additive 3. Then, the particulate solid additive 2 is added to the first homogeneous mixture to obtain a second heterogeneous mixture containing the polyolefin solid 2, the particulate solid additive 2, and the liquid additive 3. Using a RESODYN Acoustic Mixer (LabRAM Mixer), the second heterogeneous mixture is acoustically mixed at 23 - 26 °C for 2 minutes to prepare a second homogeneous mixture containing the polyolefin solid 2, the particulate solid additive 2, and the liquid additive 3.

[0090] Example of Invention 3 (IE3): In an acoustic mixer, a homogeneous mixture is prepared by acoustically mixing a polyolefin solid 2, liquid additives 3 and 4, and a particulate solid additive 2. 160 g of the polyolefin solid 2 and the liquid additive 4 are added to a glass bottle to prepare a first heterogeneous mixture containing the polyolefin solid 2 and the liquid additive 4. Using a RESODYN Acoustic Mixer (LabRAM Mixer), the contents of the bottle are acoustically mixed at 23 - 26 °C for 2 minutes to prepare a first homogeneous mixture containing the polyolefin solid 2 and the liquid additive 4. Then, the particulate solid additive 2 and the liquid additive 3 are added to the first homogeneous mixture to obtain a second heterogeneous mixture containing the polyolefin solid 2, the particulate solid additive 2, and the liquid additives 3 and 4. Using a RESODYN Acoustic Mixer (LabRAM Mixer), the second heterogeneous mixture is acoustically mixed at 23 - 26 °C for 2 minutes to prepare a second homogeneous mixture containing the polyolefin solid 2, the particulate solid additive 2, and the liquid additives 3 and 4.

[0091] Inventive Example 4 (IE4): In an acoustic mixer, a homogeneous mixture is produced by acoustically mixing a polyolefin solid 3, a liquid additive 3, and a particulate solid additive 2. Replace the polyolefin solid 2 with an equal weight of polyolefin solid 3, and replicate the procedure of IE2, except for producing a first homogeneous mixture containing polyolefin solid 3 and liquid additive 3, a second heterogeneous mixture containing polyolefin solid 3, particulate solid additive 2, and liquid additive 3, and a second homogeneous mixture containing polyolefin solid 3, particulate solid additive 2, and liquid additive 3.

[0092] Inventive Example 5 (IE5): To the polyolefin solid 2 immersed in the obtained liquid additive 4 of CE2, a particulate solid additive 2 and a liquid additive 3 were added to obtain a heterogeneous mixture. Using a RESODYN Acoustic Mixer (LabRAM Mixer), the heterogeneous mixture was acoustically mixed at 23 - 26 °C for 2 minutes to produce a first homogeneous mixture of polyolefin solid 2, particulate solid additive 2, and liquid additives 3 and 4. [Table 2]

[0093] In Table 2, the homogeneous compositions of CE2, IE3, and IE5 contained a scorch retardant (OTES), while the homogeneous compositions IE2 and IE4 did not contain a scorch retardant (OTES). In Table 2, the effectiveness of acoustic mixing in producing homogeneous compositions in IE2 - IE5 was similar to the immersion method of CE2, but the acoustic mixing method achieved homogeneity in substantially less time and at substantially lower temperatures. Also, the acoustic mixing method was effective in producing homogeneous mixtures in dry pellet or powder form.

[0094] Inventive Examples 6 to 11 (IE6 to IE11): In an acoustic mixer, a homogeneous mixture is produced by acoustically mixing polyolefin solid 1, liquid additives 2 and 3, particulate solid additive 2, and optionally liquid additive 1. 160 g of polyolefin solid 1 and liquid additives 2 and 3, particulate solid additive 2, and optionally liquid additive 1 are added to a glass bottle to produce a heterogeneous mixture containing polyolefin solid 1, liquid additives 2 and 3, particulate solid additive 2, and optionally liquid additive 1, and the contents of the bottle are acoustically mixed at 23 to 26 °C for 1 minute using a RESODYN Acoustic Mixer (LabRAM Mixer) to produce a homogeneous mixture containing polyolefin solid 1, liquid additives 2 and 3, particulate solid additive 2, and optionally liquid additive 1. [Table 3]

[0095] Table 3 shows the results of testing a homogeneous mixture of IE6 - IE11 in an MDR at 160 °C for 60 minutes, followed by an additional 30 minutes at 200 °C. The total increase in MDR torque (“delta torque”) over the 90 - minute period was calculated, and this calculated value serves as an indicator of the degree of cross - linking due to thermal decomposition of the peroxide (which results in peroxide cross - linking via carbon - carbon bonds) and / or decomposition of particulate solid additive 2 (ATH), which leads to in - situ water generation, and thus silane cross - linking via hydrolysis and condensation reactions when liquid additive 1 (VTMS) is grafted onto polyethylene. At a 0.05 wt% loading of liquid additive 2 (DCP), there was little or no difference in delta torque with and without liquid additive 1 (VTMS). However, when the amount of liquid additive 2 (DCP) was increased up to 0.2 wt%, it was observed that the homogeneous mixture containing liquid additive 1 (VTMS) showed progressively larger values of delta torque compared to the corresponding formulation without liquid additive 1 (VTMS). Without being bound by theory, the delta torque values observed without liquid additive 1 (VTMS) are thought to be due only to carbon - carbon bond formation / cross - linking promoted by the peroxide (liquid additive 2 (DCP)), and the delta torque values observed in the presence of liquid additive 1 (VTMS) are thought to be due to a combination of carbon - carbon cross - linking promoted by the peroxide (liquid additive 2 (DCP)) and silane cross - linking promoted by moisture. At any given peroxide (liquid additive 2 (DCP)) loading, the difference between the plots of delta torque vs. MDR time lines reflects the additional contribution of silane cross - linking relative to peroxide cross - linking only. These data indicate that as the amount of liquid additive 2 (DCP) in the homogeneous mixture increased, the grafting efficiency of liquid additive 1 (VTMS) increased. After these MDR evaluations, the resulting materials ranged from thermoplastic (with low delta torque values) to thermosetting (with higher delta torque values). This application provides, for example, the following inventions. [1] A method of producing a homogeneous mixture of a polyolefin solid and a liquid additive without melting the polyolefin solid during production, the method comprising applying acoustic energy at a frequency of 20 to 100 Hertz (Hz) to a first heterogeneous mixture comprising at least one liquid additive and a polyolefin solid for a time and acoustic intensity effective to substantially mix the at least one liquid additive and the polyolefin solid together while maintaining the temperature of the first heterogeneous mixture above the freezing point of the at least one liquid additive and below the melting temperature of the polyolefin solid, thereby producing a first homogeneous mixture comprising the polyolefin solid and the at least one liquid additive without melting the polyolefin solid. [2] The method according to [1] above, wherein the applying step is characterized by any one of features (i) to (v): (i) the frequency is 50 to 70 Hz, (ii) the time is 0.5 minutes to 4 hours, (iii) both (i) and (ii), (iv) maintaining the temperature of the first heterogeneous mixture below the melting temperature of the polyolefin solid comprises maintaining the temperature of the first heterogeneous mixture at 10 to 109 °C, (v) both (iv) and any one of (i) to (iii). [3] The method according to [1] or [2] above, wherein the polyolefin solid of the first heterogeneous mixture is characterized by a physical form that is powder, granules, or pellets and a melting temperature that is 61 to 180 °C, the at least one liquid additive of the first heterogeneous mixture is characterized by a freezing point below 20 °C or a melting point of 20 to 99 °C, and the first heterogeneous mixture is maintained at a temperature above the freezing point or melting point of the at least one liquid additive and below 110 °C during the applying step. [4] The polyolefin of the polyolefin solid is a polyethylene homopolymer, an ethylene / alpha-olefin copolymer, a (hydrolyzable silyl group)-functional polyethylene copolymer (HSG-FP copolymer), an ethylene / unsaturated carboxylic acid ester copolymer, or a blend of any two or more thereof. The method according to any one of [1] to [3] above. The polyolefin can be a (hydrolyzable silyl group)-functional polyethylene copolymer (HSG-FP copolymer). [5] The at least one liquid additive is additive (B) liq ~(I) liq :(B) liq liquid silanol condensation catalyst, (C) liq liquid antioxidant, (D) liq liquid colorant, (E) liq liquid scorch retarder, (F) liq liquid stabilizer (UV stabilizer) for stabilizing the homogeneous mixture against the influence of ultraviolet rays, (G) liq liquid processing aid, (H) liq liquid flame retardant, and (I) liq any one or more of the liquid polymers other than (A). The method according to any one of [1] to [4] above. [6] The first heterogeneous mixture further includes at least one particulate solid additive different from the polyolefin solid, and the first homogeneous mixture further includes the at least one particulate solid additive. The method according to any one of [1] to [5] above. [7] Before the applying step, a contacting step (i) or (ii): (i) contacting the polyolefin solid with the at least one liquid additive to produce the first heterogeneous mixture, or (ii) contacting the polyolefin solid with a low melting point solid additive having a melting point of 25 to 110 °C to produce a heterogeneous solid preliminary mixture, and melting the low melting point solid additive without melting the polyolefin solid to produce the first heterogeneous mixture. The method according to any one of [1] to [6] above, further including producing the first heterogeneous mixture. [8] contacting the first homogeneous mixture with at least one particulate solid additive different from the polyolefin solid to produce a second heterogeneous mixture comprising the first homogeneous mixture and the at least one particulate solid additive; and then applying acoustic energy at a frequency of 20 to 100 Hz and an acoustic intensity effective to mix them together while maintaining the temperature of the second heterogeneous mixture above the freezing point of the at least one liquid additive and below the melting temperature of the polyolefin solid, thereby producing a second homogeneous mixture comprising the polyolefin solid, the at least one liquid additive, and the at least one particulate solid additive without melting the polyolefin polymer solid during the producing step, the method according to any one of [1] to [7] above further comprising. [9] further comprising melting the polyolefin solid of the homogeneous mixture to produce a molten mixture; shaping the molten mixture to obtain a shaped molten mixture; and cooling the shaped molten mixture to obtain a shaped solid, the method according to any one of [1] to [8] above.

[10] The method according to [9] above, wherein the shaping step comprises extruding the molten mixture as a coating onto a conductive core and solidifying the coating to produce a coated conductor comprising the conductive core and a coating shaped solid at least partially covering the conductive core.

[11] The method according to [9] or

[10] above, further comprising curing the polyolefin of the shaped solid to obtain a shaped cured product.

[12] A shaped cured product prepared by the method according to

[11] above.

Claims

1. A method for producing a homogeneous mixture of a polyolefin solid and a liquid additive without melting the polyolefin solid during production, the method comprising: Applying acoustic energy at a frequency of 20 to 100 Hertz (Hz) to a first heterogeneous mixture comprising at least one liquid additive and a polyolefin solid, with an effective time and acoustic intensity to substantially mix the at least one liquid additive and the polyolefin solid together, while maintaining the temperature of the first heterogeneous mixture above the freezing point of the at least one liquid additive and below the melting temperature of the polyolefin solid; Thereby producing a first homogeneous mixture comprising the polyolefin solid and the at least one liquid additive without melting the polyolefin solid comprising, The liquid additive is added to the polyolefin solid as a neat liquid, and the heterogeneous mixture does not contain a liquid solvent, The polyolefin of the polyolefin solid is a polyethylene homopolymer, an ethylene / alpha-olefin copolymer, a (hydrolyzable silyl group)-functionalized polyethylene copolymer (HSG-FP copolymer), an ethylene / unsaturated carboxylic acid ester copolymer, or any blend of two or more thereof, method.

2. The method according to claim 1, wherein the applying step is characterized by any one of features (i) to (v): (i) the frequency is from 50 to 70 Hz; (ii) the time is from 0.5 minutes to 4 hours; (iii) both (i) and (ii); (iv) maintaining the temperature of the first heterogeneous mixture below the melting temperature of the polyolefin solid includes maintaining the temperature of the first heterogeneous mixture at 10 to 109 °C; and both of any one of (v), (iv), and (i) to (iii).

3. the polyolefin solid of the first heterogeneous mixture is characterized by a physical form that is powder, granules, or pellets, and by a melting temperature that is 61 to 180 °C, the at least one liquid additive of the first heterogeneous mixture is characterized by a freezing point below 20 °C or by a melting point of 20 to 99 °C, the first heterogeneous mixture is maintained at a temperature above the freezing point or melting point of the at least one liquid additive and below 110 °C during the application step, The method according to claim 1 or 2.

4. the at least one liquid additive is additive (B) ｌｉｑ to (I) ｌｉｑ : (B) ｌｉｑ liquid silanol condensation catalyst, (C) ｌｉｑ liquid antioxidant, (D) ｌｉｑ liquid colorant, (E) ｌｉｑ liquid scorch retardant, (F) ｌｉｑ liquid stabilizer (UV stabilizer) for stabilizing the homogeneous mixture against the effects of ultraviolet light, (G) ｌｉｑ liquid processing aid, (H) ｌｉｑ liquid flame retardant, and (I) any one or more of liquid polymers that are not the polyolefin, The method according to any one of claims 1 to 3.

5. the first heterogeneous mixture further comprises at least one particulate solid additive different from the polyolefin solid, and the first homogeneous mixture further comprises the at least one particulate solid additive, The method according to any one of claims 1 to 4.

6. Before the application step, a contacting step (i) or (ii): (i) contacting the polyolefin solid with the at least one liquid additive to produce the first heterogeneous mixture, or (ii) contacting the polyolefin solid with a low melting point solid additive having a melting point of 25 to 110°C to produce a heterogeneous solid premix, melting the low melting point solid additive without melting the polyolefin solid, and producing the first heterogeneous mixture by producing the first heterogeneous mixture The method according to any one of claims 1 to 5, further comprising.

7. contacting the first homogeneous mixture with at least one particulate solid additive different from the polyolefin solid to produce a second heterogeneous mixture comprising the first homogeneous mixture and the at least one particulate solid additive; Then applying acoustic energy at a frequency of 20 to 100 Hz and an acoustic intensity effective to substantially mix them together while maintaining the temperature of the second heterogeneous mixture above the freezing point of the at least one liquid additive and below the melting temperature of the polyolefin solid; thereby producing a second homogeneous mixture comprising the polyolefin solid, the at least one liquid additive, and the at least one particulate solid additive without melting the polyolefin polymer solid during the producing step; The method according to any one of claims 1 to 6, further comprising.

8. melting the polyolefin solid of the homogeneous mixture to produce a molten mixture; shaping the molten mixture to obtain a shaped molten mixture; cooling the shaped molten mixture to obtain a shaped solid; The method according to any one of claims 1 to 7, further comprising.

9. The method of claim 8, wherein the shaping step comprises extruding the molten mixture as a coating onto a conductive core and solidifying the coating to produce a coated conductor comprising the conductive core and a coating shaped solid at least partially covering the conductive core.

10. The method according to claim 8 or 9, further comprising curing the polyolefin of the shaped solid to obtain a shaped cured product.

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