阅读说明：本技术 含有氧化膦的基于乙烯的聚合物组合物 (Ethylene-based polymer compositions containing phosphine oxides ) 是由 B·乔杜里 J·柯吉恩 C·利奥塔 P·波利特 S·萨尔格达达兰 于 2019-09-12 设计创作，主要内容包括：本发明提供一种组合物。所述组合物包含(i)基于乙烯的聚合物；(ii)有机过氧化物,(iii)氧化膦,和(iv)质子酸源化合物(“PASC”),其选自：质子酸、质子酸-产生剂化合物(“PAGC”)和其组合。本发明还提供一种涂层导体。所述涂层导体包含导体和所述导体上的涂层,所述涂层含有组合物,所述组合物包含(i)基于乙烯的聚合物；(ii)有机过氧化物,(iii)氧化膦,和(iv)质子酸源化合物(“PASC”),其选自：质子酸、质子酸-产生剂化合物(“PAGC”)和其组合。(The present invention provides a composition. The composition comprises (i) an ethylene-based polymer; (ii) (ii) an organic peroxide, (iii) a phosphine oxide, and (iv) a protonic acid source compound ("PASC") selected from the group consisting of: protic acids, protic acid-generator compounds ("PAGC"), and combinations thereof. The invention also provides a coated conductor. The coated conductor comprises a conductor and a coating on the conductor, the coating comprising a composition comprising (i) an ethylene-based polymer; (ii) (ii) an organic peroxide, (iii) a phosphine oxide, and (iv) a protonic acid source compound ("PASC") selected from the group consisting of: protic acids, protic acid-generator compounds ("PAGC"), and combinations thereof.)

1. A composition, comprising:

(i) an ethylene-based polymer;

(ii) an organic peroxide;

(iii) a phosphine oxide; and

(iv) a protic acid source compound ("PASC") selected from the group consisting of: protic acids, protic acid-generator compounds ("PAGC"), and combinations thereof.

2. The composition of claim 1, wherein the phosphine oxide has the structure (1):

wherein R is¹、R²And R³Each independently selected from the group consisting of: c₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Heterohydrocarbyl and combinations thereof;

with the proviso that the phosphorus atom is bound to each R¹、R²And R³To the carbon atom in (b).

3. The composition of claim 1 or 2, wherein the PASC is the protic acid; and is

The composition has a percentage of retained peroxide of 2% to 100% after heating at 100 ℃ for 2 hours.

4. The composition according to any one of claims 1 to 3, wherein the PASC is the protic acid, and the protic acid is selected from the group consisting of: sulfonic acids, sulfenic acids, sulfinic acids, carboxylic acids, phosphorus-based acids, and combinations thereof.

5. The composition according to claim 1, wherein the PASC is the PAGC and the PAGC comprises an Antioxidant (AO).

6. The composition according to claim 5, wherein said AO is a sulfur-based antioxidant.

7. The composition according to any one of claims 2 to 5, wherein R¹、R²And R³Each independently selected from the group consisting of: phenyl, n-octyl and 2, 4, 6-trimethylbenzoyl.

8. The composition of claim 7, wherein R¹、R²And R³The same is true.

9. The composition according to any one of claims 1 to 8, wherein the organic peroxide is dicumyl peroxide.

10. The composition of any one of claims 2 to 9, wherein the composition comprises from 0.001 to 1.0 weight percent of the phosphine oxide having structure (1), based on the total weight of the composition; and is

R¹、R²And R³Each is phenyl.

11. The composition of any one of claims 2 to 9, wherein the composition comprises from 0.001 to 1.0 weight percent of the phosphine oxide having structure (1), based on the total weight of the composition; and is

R¹、R²And R³Each is n-octyl.

12. The composition of any one of claims 2 to 9, wherein the composition comprises from 0.001 to 1.0 weight percent of the phosphine oxide having structure (1), based on the total weight of the composition, and

(i)R¹and R²Each is phenyl and R³Is 2, 4, 6-trimethylbenzoyl; or

(ii)R¹And R³Each is 2, 4, 6-trimethylbenzoyl and R²Is phenyl.

13. The composition of claim 1, wherein the PASC is PAGC; and is

The retained MH of the composition after 21 days of heating at 70 ℃ was 100%.

14. A crosslinked product made by heating the composition of any one of claims 1 to 13 to a temperature sufficient to crosslink the composition.

15. A coated conductor, comprising:

a conductor; and

a coating on the conductor, the coating comprising the composition of any one of claims 1 to 13 or the crosslinked product of claim 14.

Technical Field

The present invention relates to crosslinkable compositions and coated conductors comprising the same.

Disclosure of Invention

Crosslinkable compositions comprising an ethylene-based polymer and an organic peroxide are frequently used to form coatings, and in particular for insulating or jacketing layers for wires and cables. However, it is known that protic acids which may be contained in or generated by additives in the crosslinkable composition, such as antioxidants, cause premature decomposition of the organic peroxide by non-productive routes to the crosslinking crosslinkable composition. That is, when the composition is stored over time, or when the composition is extruded onto a conductor, the organic peroxide decomposes in an ionic pathway that does not result in the desired free radical crosslinking reaction. Without retaining sufficient amounts of organic peroxide in the composition during storage and extrusion, the composition cannot be crosslinked during subsequent continuous vulcanization steps that occur after extrusion to make a coated conductor, making the coated conductor unsuitable for wire and cable applications.

We have recognized a need for coating compositions containing ethylene-based polymers, organic peroxides, and protonic acid source compounds suitable for wire and cable applications. We have further recognized that there is a need for a coating composition containing an ethylene-based polymer, an organic peroxide, and a protonic acid source compound that prevents or slows the ionic decomposition of the organic peroxide during storage or at extrusion temperatures of about 140 ℃ or less, such that the composition retains an amount of the organic peroxide that subsequently enables the coating composition to crosslink during continuous vulcanization (at temperatures greater than about 140 ℃).

The present invention provides a composition. The composition comprises: (i) an ethylene-based polymer; (ii) (ii) an organic peroxide, (iii) a phosphine oxide, and (iv) a protonic acid source compound ("PASC") selected from the group consisting of: protic acids, protic acid-generator compounds ("PAGC"), and combinations thereof.

The invention also provides a coated conductor. The coated conductor comprises a conductor and a coating on the conductor, the coating comprising a composition. The composition comprises: (i) an ethylene-based polymer; (ii) (ii) an organic peroxide, (iii) a phosphine oxide, and (iv) a protonic acid source compound ("PASC") selected from the group consisting of: protic acids, protic acid-generator compounds ("PAGC"), and combinations thereof.

The present invention also provides a crosslinked product prepared by heating a composition to a temperature sufficient to crosslink the composition. The crosslinked product may be a coating on a conductor.

Definition of

Any reference to the periodic table of elements is the periodic table of elements published by CRC Press, inc., 1990-1991. Reference to the element groups in this table is made by numbering the new symbols of the groups.

For purposes of united states patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or the equivalent US version thereof is so incorporated by reference), especially with respect to the disclosure of definitions in the art (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge.

The numerical ranges disclosed herein include all values from the lower and upper values, and include the lower and upper values. For ranges containing exact values (e.g., ranges of 1 or 2 or 3 to 5 or 6 or 7), any subrange between any two exact values is included (e.g., the above range 1 to 7 includes the subranges 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

Unless stated to the contrary, implied from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.

Any examples disclosed herein are non-limiting.

"Alkyl (Alkyl)" and "Alkyl group" refer to saturated linear, cyclic or branched hydrocarbon groups.

"Alpha-olefin/Alpha-olefin" and like terms refer to a hydrocarbon molecule or a substituted hydrocarbon molecule (i.e., a hydrocarbon molecule that includes one or more atoms other than hydrogen and carbon, such as halogen, oxygen, nitrogen, etc.), the hydrocarbon molecule including (i) only one ethylenic unsaturation, between a first and a second carbon atom, and (ii) at least 2 carbon atoms, or 3 to 20 carbon atoms, or 4 to 10 carbon atoms, or 4 to 8 carbon atoms. Examples of the α -olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-dodecene and mixtures of two or more of these monomers.

"antioxidant" refers to the type or class of compounds that can be used to minimize oxidation that may occur during polymer processing.

"blend," "polymer blend," and similar terms refer to a composition of two or more polymers. Such blends may be miscible or immiscible. Such blends may or may not be phase separated. Such blends may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, x-ray scattering, and any other method for measuring and/or identifying domain configurations.

A "cable" is a protective insulation, sheath, at least one conductor within a sheath, such as a wire, an optical fiber, and the like. A cable may be two or more wires or two or more optical fibers bound together in a common protective sheath or sheath. The combination cable may contain both electrical wires and optical fibers. The individual wires or fibers within the sheath or sheath may be bare, covered or insulated. Typical cable designs are described in USP 5,246,783; 6,496,629; and 6,714,707. The cable may be designed for low, medium and/or high voltage applications.

"Carboxylic acid" is an organic acid containing a carboxyl group (-COOH).

The term "composition" refers to a mixture of materials comprising the composition as well as reaction products and decomposition products formed from the materials of the composition.

The terms "comprising," "including," "having," and derivatives thereof, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant or compound, whether polymeric or otherwise. In contrast, the term "consisting essentially of … …" excludes any other components, steps, or procedures from any subsequently recited range, except for components, steps, or procedures that are not necessary for operability. The term "consisting of … …" excludes any component, step, or procedure not specifically recited or recited. Unless otherwise specified, the term "or" means the members listed individually as well as in any combination. The use of the singular includes the use of the plural and vice versa.

A "conductor" is one or more wires or one or more optical fibers for conducting heat, light and/or electricity at any voltage (DC, AC or transient). The conductor may be a single wire/fiber or a plurality of wires/fibers and may be linear or tubular. Non-limiting examples of suitable conductors include carbon and various metals such as silver, gold, copper, and aluminum. The conductor may also be an optical fiber made of glass or plastic. The conductor may or may not be disposed in a protective sheath. The conductor may be a single cable or multiple cables (i.e., cable cores or cores) bound together.

"crosslinkable" and "curable" mean that the polymer is uncured or crosslinked, and has not been subjected to or exposed to a treatment that has initiated substantial crosslinking, either before or after being shaped into an article, although the polymer may include additives or functional groups that will effect substantial crosslinking upon being subjected to or exposed to such treatment (e.g., exposure to heat). The crosslinkability of a polymer or composition can be evaluated by testing and measuring the change in elastic torque in a Moving Die Rheometer (MDR) at elevated temperatures.

"crosslinking" and like terms mean that the polymer composition has xylene or decalin extractables of less than or equal to 90 weight percent (i.e., greater than or equal to 10 weight percent gel content) before or after being shaped into an article.

"curing" and like terms means that the polymer is subjected or exposed to a treatment that initiates crosslinking either before or after being shaped into an article.

An "ethylene-based polymer," "ethylene polymer," or "polyethylene" is a polymer that contains an amount of polymerized ethylene equal to or greater than 50 weight percent, or a majority amount, based on the weight of the polymer, and optionally may include one or more comonomers. Thus, the generic term "ethylene-based polymer" encompasses both ethylene homopolymers and ethylene interpolymers. Suitable comonomers are alpha-olefins. "ethylene-based polymer" and the term "polyethylene" may be used interchangeably. Examples of ethylene-based polymers (polyethylenes) include Low Density Polyethylene (LDPE) and linear polyethylenes. Examples of linear polyethylenes include Linear Low Density Polyethylene (LLDPE), Ultra Low Density Polyethylene (ULDPE), Very Low Density Polyethylene (VLDPE), multicomponent ethylene-based copolymer (EPE), ethylene/alpha-olefin multi-block copolymer (also known as Olefin Block Copolymer (OBC)), single site catalyzed linear low density polyethylene (m-LLDPE), substantially linear or linear plastomer/elastomer, Medium Density Polyethylene (MDPE), and High Density Polyethylene (HDPE). Generally, polyethylene can be produced in a gas phase fluidized bed reactor, a liquid phase slurry process reactor, or a liquid phase solution process reactor using a heterogeneous catalyst system, such as a Ziegler-Natta catalyst (Ziegler-Natta catalyst), a homogeneous catalyst system comprising a group 4 transition metal and a ligand structure, such as a metallocene, a non-metallocene metal center, a heteroaryl, a heterovalent aryloxyether, a phosphinimine, and the like. Combinations of heterogeneous and/or homogeneous catalysts may also be used in single reactor or dual reactor configurations. Polyethylene can also be produced in a high pressure reactor without catalyst.

An "ethylene/α -olefin polymer" is a polymer that contains a majority amount of polymerized ethylene, based on the weight of the polymer, and one or more α -olefin comonomers.

"ethylene multi-block interpolymer," "ethylene multi-block copolymer" (or "OBC"), and similar terms, refer to ethylene-based polymers that comprise two or more chemically distinct regions or segments (referred to as "blocks") preferably joined in a linear fashion, that is, a polymer comprising chemically distinct units joined end-to-end with respect to polymeric ethylenic functionality, rather than joined in a pendant or grafted fashion. In a preferred embodiment, the blocks differ in the following respects: the amount or type of comonomer incorporated, the density of the polymer attributable to such composition, the amount of crystallinity, crystallite size, type or degree of stereoisomerism (isotactic or syndiotactic), regioregularity or regioirregularity, amount of branching (including long chain branches or hyper-branches), homogeneity or any other chemical or physical property. In contrast to prior art block interpolymers, including interpolymers produced by sequential monomer addition, rheological catalysts, or anionic polymerization techniques, in preferred embodiments, the multiblock copolymers are characterized by polymer polydispersity (PDI or M) due to the effect of the shuttling agent and the multiple catalysts used in their preparation_w/M_nOr MWD), block length distribution, and/or unique distribution of block number distribution. Representative ethylene multi-block interpolymers include those available under The trademark INFUSE from The Dow Chemical Company^TMEthylene multi-block interpolymers, made and sold.

An "ethylene plastomer/elastomer" is a substantially linear or linear ethylene/alpha-olefin copolymer containing a homogeneous short chain branching distribution comprising units derived from ethylene and units derived from at least one C3-C10 alpha-olefin comonomer or at least one C4-C8 alpha-olefin comonomer or at least one C6-C8 alpha-olefin comonomer. The ethylene plastomer/elastomer has a density of from 0.870g/cc, or 0.880g/cc, or 0.890g/cc to 0.900g/cc, or 0.902g/cc, or 0.904g/cc, or 0.909g/cc, or 0.910g/cc, or 0.917 g/cc. Examples of ethylene plastomers/elastomers include AFFINITY^TMPlastomers and elastomers (available from Dow chemical Co., Ltd.), EXACT^TMPlastomers (available from ExxonMobil Chemical), Tafmer^TM(commercially available from Mitsui), Nexlene^TM(available from SK Chemicals Co.) and Lucene^TM(available from LG Chemie Ltd.).

"functional group" and like terms refer to an atomic moiety or group that is responsible for imparting a characteristic reaction to a particular compound. Examples of functional groups include heteroatom-containing moieties, oxygen-containing moieties (e.g., hydrolyzable silane, alcohol, aldehyde, ester, ether, ketone, and peroxide groups), and nitrogen-containing moieties (e.g., amide, amine, azo, imide, imine, nitrate, nitrile, and nitrate groups).

A "heteroatom" is an atom other than carbon or hydrogen. The heteroatoms may be non-carbon atoms of groups IV, V, VI and VII of the periodic Table of the elements. Examples of heteroatoms include: F. n, O, P, B, S and Si.

A "high density polyethylene" (or "HDPE") is an ethylene homopolymer or an ethylene/alpha-olefin copolymer having at least one C4-C10 alpha-olefin comonomer or C4 alpha-olefin comonomer and having a density greater than 0.94g/cc, or 0.945g/cc, or 0.95g/cc, or 0.955g/cc to 0.96g/cc, or 0.97g/cc, or 0.98 g/cc. The HDPE may be a unimodal copolymer or a multimodal copolymer. A "unimodal ethylene copolymer" is an ethylene/C copolymer having one distinct peak in Gel Permeation Chromatography (GPC) showing molecular weight distribution₄-C₁₀An alpha-olefin copolymer. A "multimodal ethylene copolymer" is an ethylene/C copolymer having at least two distinct peaks in GPC showing the molecular weight distribution₄-C₁₀An alpha-olefin copolymer. Multimodal includes copolymers having two peaks (bimodal) as well as copolymers having more than two peaks. Examples of HDPE include DOW^TMHigh Density Polyethylene (HDPE) resin (available from Dow chemical), ELITE^TMReinforced polyethylene resin (available from Dow chemical Co., Ltd.), CONTINUUM^TMBimodal polyethylene resin (available from Dow chemical Co., Ltd.), LUPOLEN^TM(available from LyondellBasell, Debarsel) and HDPE products from Borealis, Ineos and Exxon Mobil.

The terms "hydrocarbyl" and "hydrocarbon" refer to substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic or acyclic species. Examples include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, and alkynyl-groups. The term "heterohydrocarbyl" refers to substituents containing hydrogen, carbon, and heteroatoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic, or acyclic species.

The "jacket" is the outermost coating on the conductor.

"Linear Low Density polyethylene" (or "LLDPE") is a linear ethylene/alpha-olefin copolymer containing a heterogeneous short chain branching distribution comprising units derived from ethylene and units derived from at least one C₃-C₁₀Alpha-olefin comonomer or at least one C₄-C₈Alpha-olefin comonomer or at least one C₆-C₈Units of an alpha-olefin comonomer. LLDPE is characterized by few, if any, long chain branches compared to conventional LDPE. The LLDPE has a density of from 0.916g/cc to 0.925 g/cc. Examples of LLDPE include TUFLIN^TMLinear low density polyethylene resin (available from Dow chemical Co.), DOWLEX^TMPolyethylene resin (available from Dow chemical Co., Ltd.), MARLEX^TMPolyethylene (available from Chevron Phillips) and AXELERON^TMGP 6059CPD (available from the Dow chemical company).

"Low density polyethylene" (or "LDPE") is an ethylene homopolymer or an ethylene/alpha-olefin copolymer comprising at least one C₃-C₁₀Alpha-olefins, or C₃-C₄An alpha-olefin having a density of from 0.915g/cc to 0.925g/cc and containing long chain branches having a broad MWD. LDPE is typically produced by means of high pressure free radical polymerisation (tubular reactor or autoclave with free radical initiator). Examples of LDPE include MarFlex^TM(Chevrolet Philips), LUPOLEN^TM(Lyocell), and LDPE products from Borealis, Ineos, Exxon Mobil, and the like.

"Medium density polyethylene" (or "MDPE") is an ethylene homopolymer orAn ethylene/alpha-olefin copolymer comprising at least one C₃-C₁₀Alpha-olefins, or C₃-C₄An alpha-olefin having a density of from 0.926g/cc to 0.940 g/cc. Examples of suitable MDPE include AXELERON^TMFO 6548BK CPD、AXELERON^TM FO 6549NT CPD、AXELERON^TMFO 8864NT CPD and AXELERON^TMFO 8864BK CPD, each available from the Dow chemical company.

"multicomponent ethylene-based copolymers" (or "EPEs") include units derived from ethylene and units derived from at least one C3-C10 alpha-olefin comonomer, at least one C4-C8 alpha-olefin comonomer, or at least one C6-C8 alpha-olefin comonomer, as described in patent references USP 6,111,023; USP 5,677,383; and USP 6,984,695. The EPE resin has a density of 0.905g/cc, or 0.908g/cc, or 0.912g/cc, or 0.920g/cc to 0.926g/cc, or 0.929g/cc, or 0.940g/cc, or 0.962 g/cc. Examples of the EPE resin include ELITE^TMReinforced polyethylene (available from Dow chemical Co.), ELITE AT^TMAdvanced technology resins (available from the Dow chemical company), SURPASS^TMPolyethylene (PE) resins (available from Nova Chemicals) and SMART^TM(available from SK chemical Co.).

An "olefin-based polymer" or "polyolefin" is a polymer that contains equal to or greater than 50 weight percent or a majority amount of polymerized olefin monomer (based on the total weight of the polymer) and optionally may contain at least one comonomer. Examples of alpha-olefin monomers include C₂Or C₃To C₄Or C₆Or C₈Or C₁₀Or C₁₂Or C₁₆Or C₁₈Or C₂₀Alpha-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. Examples of the olefin-based polymer include ethylene-based polymers and propylene-based polymers.

A "polymer" is a polymeric compound prepared by polymerizing monomers of the same or different types. Thus, the generic term polymer encompasses the term "homopolymer" (used to refer to polymers prepared from only one type of monomer, with the understanding that minor amounts of impurities may be incorporated into the polymer structure), as well as the term "interpolymer," which comprises a copolymer (used to refer to polymers prepared from two different types of monomers), a terpolymer (used to refer to polymers prepared from three different types of monomers), and polymers prepared from more than three different types of monomers. Minor amounts of impurities, for example, catalyst residues, may be incorporated into and/or within the polymer. It also encompasses all forms of copolymers, such as random, block, and the like. The terms "ethylene/a-olefin polymer" and "propylene/a-olefin polymer" indicate copolymers as described above prepared by polymerizing ethylene or propylene, respectively, with one or more additional polymerizable a-olefin comonomers. It should be noted that although a polymer is often referred to as being "composed of" one or more specific monomers, "containing" a specific monomer content, or the like, based on "a specific monomer or monomer type, in this case, the term" monomer "refers to the polymerized residue of a specific monomer and does not refer to an unpolymerized species. In general, a polymer herein refers to a "unit" based on polymerized form of the corresponding monomer.

"sheath" is a generic term and when used in relation to a cable, it encompasses insulating coverings or layers, protective jacketing, and the like.

"ultra-low density polyethylene" (or "ULDPE") and "very low density polyethylene" (or "VLDPE") are each linear ethylene/alpha-olefin copolymers containing a heterogeneous short chain branching distribution comprising units derived from ethylene and units derived from at least one C₃-C₁₀Alpha-olefin comonomer, at least one C₄-C₈Alpha-olefin comonomer or at least one C₆-C₈Units of an alpha-olefin comonomer. ULDPE and VLDPE each have a density of 0.885g/cc or 0.90g/cc to 0.915 g/cc. Examples of ULDPE and VLDPE include ATTANE^TMUltra low density polyethylene resin (available from Dow chemical) and FLEXOMER^TMVery low density polyethylene resins (available from the dow chemical company).

A "wire" is a single strand of electrically conductive metal, such as copper or aluminum, or a single strand of optical fiber.

Test method

Density is measured according to ASTM D792, method B. Results are in grams (g)/cubic centimeter (g/cc or g/cm)³) Is recorded in units.

Melting points (Tm) are measured by Differential Scanning Calorimetry (DSC) techniques for measuring the melting peak of polyolefins, as described in USP 5,783,638. Melting points are reported in degrees Celsius (. degree. C.).

Retention of peroxide percentage

The "percent peroxide retained" is the amount of organic peroxide present in the composition after exposure to 100 ℃ for a period of time (0.5 hours, 1.0 hours, 1.5 hours, or 2.0 hours) as compared to the amount of organic peroxide present in the same composition after 2 minutes of adjustment at 100 ℃ (i.e., the initial amount of peroxide before significant decomposition of the organic peroxide occurs).

Sample solutions containing dicumyl peroxide (DCP), dodecylbenzene sulfonic acid (DBSA), phosphine oxide, and dodecane (to simulate an ethylene-based polymer) were formed in 6 dram glass vials. The solution was stirred with a magnetic stir bar. In the case of photosensitive phosphine oxides such as diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, amber vials are used to avoid the effects of light.

The glass vial was immersed in a well-stirred (500rpm) silicon oil bath maintained at a temperature of 100 ℃ on a stirring hot plate. The sample solution was heated to a temperature of 100 ℃ and held at 100 ℃ for a period of 2 minutes, 0.5 hours, 1.0 hour, 1.5 hours, and 2.0 hours while mixing. The sample solution is heated in a glass vial without a cap or cover (in other words, the sample solution is exposed to the atmosphere while being heated).

The sample solution is then analyzed after a period of 2 minutes, 0.5 hours, 1.0 hour, 1.5 hours, and 2.0 hours at 100 ℃ to determine the concentration or amount of DCP. A600. mu.l aliquot was removed from each glass vial and placed in a 1.5mL microcentrifuge tube, cooled in an ice bath for 7-10 minutes, and centrifuged at 6,000rpm in a VWR Galaxy microcentrifuge, model C1413. Then, 350 μ l of the clear fraction was removed from each aliquot and combined with 700 μ l of isopropanol and analyzed by liquid chromatography to determine the concentration of DCP present in the fraction. The amount of DCP is reported in weight% or mole% and then converted to the percentage peroxide retained. The amount of DCP in the sample solution measured after 2 minutes at 100 ℃ was referred to as the initial DCP amount.

The percent peroxide retained was calculated according to the following equation (1):

wherein t is 0.5 hour, 1.0 hour, 1.5 hours, or 2.0 hours.

Retention maximum Torque (MH)

The retained maximum torque (MH) is an indication of the final degree of crosslinking (an indication of the amount of peroxide present). MH was determined in the following manner. Moving Die Rheometer (MDR) analysis was performed on the compounds using an Alpha Technologies Rheometer model MDR 2000 unit. The tests were based on ASTM procedure D5289, Standard Test Method for Rubber-Property Vulcanization Using Rotorless Current Meters, Using a Rotorless curing Meter. MDR analysis was performed at time intervals (t) of t at 0 hours and t at day 21 using 4-5 grams of the material (compound in Table 5). The samples were tested at 180 ℃ or 182 ℃ for 20 minutes, or 140 ℃ for 120 minutes, for both temperature conditions, under 0.5 degree arc vibration. The compounds tested contained all necessary additives, including a crosslinking agent (such as an organic peroxide).

The percentage MH retained was calculated according to the following equation (2):

where t is at 70 ℃ for 21 days.

Detailed Description

The present invention provides compositions suitable for wire and cable applications. The composition comprises: (i) an ethylene-based polymer; (ii) (ii) an organic peroxide, (iii) a phosphine oxide, and (iv) a protonic acid source compound ("PASC") selected from the group consisting of: protic acids, protic acid-generator compounds ("PAGC"), and combinations thereof.

In one embodiment, the composition comprises (i) an ethylene-based polymer; (ii) (ii) an organic peroxide, (iii) a phosphine oxide, and (iv) a PASC selected from the group consisting of: protic acids, PAGC, and combinations thereof; and (v) optionally additives.

In one embodiment, the phosphine oxide is a compound having the following structure (1):

wherein R is¹、R²And R³Each independently selected from C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Heterohydrocarbyl and combinations thereof;

with the proviso that the phosphorus atom is bound to each R¹、R²And R³To the carbon atom in (b).

i. Ethylene-based polymers

The compositions of the present invention comprise an ethylene-based polymer.

The ethylene-based polymer can be any ethylene-based polymer disclosed herein.

The ethylene-based polymer may be an ethylene homopolymer or an ethylene interpolymer. Examples of ethylene-based polymers include LDPE and linear polyethylene. Examples of linear polyethylenes include LLDPE, ULDPE, VLDPE, multicomponent ethylene-based copolymers (EPE), ethylene/alpha-olefin multi-block copolymers (also known as Olefin Block Copolymers (OBC)), single site catalyzed linear low density polyethylenes (m-LLDPE), substantially linear or linear plastomers/elastomers, MDPE and HDPE. In one embodiment, the ethylene-based polymer is selected from the group consisting of LDPE, LLDPE, ULDPE, VLDPE, EPE, OBC, m-LLDPE, substantially linear or linear plastomer/elastomer, MDPE, HDPE, and combinations thereof.

In one embodiment, the ethylene-based polymer is an ethylene/a-olefin copolymer. In another embodiment, the ethylene/alpha-olefin copolymer is ethylene/C₃-C₂₀Alpha-olefins, or ethylene/C₃-C₁₀Alpha-olefins, or ethylene/C₄-C₁₀Alpha-olefins or ethylene/C₄-C₈An alpha-olefin. Examples of suitable alpha-olefins include 1-butene, 1-hexene and 1-octene.

In one embodiment, the ethylene-based polymer is free or substantially free of styrene.

In one embodiment, the ethylene/α -olefin copolymer consists of: ethylene and C₄-C₈An alpha-olefin comonomer. In other words, ethylene/C₄-C₈The alpha-olefin copolymer contains ethylene and C₄-C₈The alpha-olefin comonomer as the only monomer unit.

The ethylene-based polymer may or may not be functionalized. The "functionalized ethylene-based polymer" comprises a functional group. In one embodiment, the functional group is pendant grafted to the polymer chain. Functional groups can also be incorporated by copolymerization of suitable monomers containing the desired functional group. Examples of suitable functional groups include halo (especially chloro and bromo), hydroxyl, carboxyl, carbonyl, phosphonyl, anhydride, amino, amine, imide, epoxy, mercapto, sulfate, sulfonate, amide, and ester groups. Examples of unsaturated carboxylic acid and anhydride compounds that can be grafted onto the preformed ethylene-based polymer include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, and itaconic anhydride. In one embodiment, the functionalized ethylene-based polymer is a maleic anhydride functionalized ethylene/a-olefin interpolymer. In another embodiment, the functionalized ethylene-based polymer is a maleic anhydride functionalized ethylene/octene interpolymer. The ethylene-based polymer may comprise one or more of the following: ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-vinyl acrylate copolymers, ethylene-acrylic acid copolymers, ethylene-vinyltrimethoxysilane copolymers or other copolymers made in a high pressure reactor and containing from 0.2 to less than 50 weight percent or 50 weight percent comonomer.

In one embodiment, the ethylene-based polymer is not functionalized.

The ethylene-based polymer contains 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt%, or 75 wt% to 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 100 wt% ethylene, based on the total weight of the ethylene-based polymer.

In one embodiment, the ethylene-based polymer contains 55 wt%, or 60 wt%, or 65 wt%, or 70 wt%, or 75 wt% to 80 wt%, or 85 wt%, or 90 wt%, or 95 wt% ethylene, based on the total weight of the ethylene-based polymer; and an inverse amount of an alpha-olefin comonomer, or 5 wt%, or 10 wt%, or 15 wt%, or 20 wt% to 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt% of an alpha-olefin comonomer.

The ethylene-based polymer may include two or more embodiments disclosed herein.

Organic peroxides

The compositions of the present invention comprise an organic peroxide. An "organic peroxide" is a compound containing at least one carbon atom having the following structure (2):

R¹-O-O-R²structure (2)

Wherein R is¹And R²Each independently selected from C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Heterohydrocarbyl, hydrogen, and combinations thereof:

with the proviso that R¹And R²Is at least one of C₁-C₄₀Hydrocarbyl or C₁-C₄₀A heterohydrocarbyl group.

Examples of suitable organic peroxides include dicumyl peroxide (DCP), lauryl peroxide, benzoyl peroxide, t-butyl perbenzoate, di (t-butyl) peroxide, cumene hydroperoxide, 2, 5-dimethyl-2, 5-di (t-butyl-peroxy) hexyne-3, 2, -5-di-methyl-2, 5-di (t-butyl-peroxy) hexane, t-butyl hydroperoxide, isopropyl percarbonate, α' -bis (t-butyl-peroxy) diisopropylbenzene, t-butyl-peroxy-2-ethylhexyl monocarbonate, 1-bis (t-butyl-peroxy) -3, 5, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-dihydroxyl peroxide, T-butyl cumyl peroxide, α' -bis (t-butylperoxy) p-diisopropylbenzene, di- (t-butylperoxyisopropyl), benzene, t-butyl cumyl peroxide, di-t-butyl peroxide, and combinations thereof.

Non-limiting examples of suitable commercially available organic peroxides include TRIGONOX from Akzo Nobel^TMAnd LUPEROX from Achima (ARKEMA)^TM。

In one embodiment, the organic peroxide is selected from dicumyl peroxide (DCP); 2, -5-dimethyl-2, 5-di (tert-butylperoxy) hexane; di- (tert-butylperoxyisopropyl) benzene; tert-butyl cumyl peroxide; di-t-butyl peroxide and combinations thereof.

In one embodiment, the organic peroxide is dicumyl peroxide (DCP).

In one embodiment, the peroxide is a dialkyl peroxide. "dialkyl peroxides" are compounds having the following structure (2A):

R¹-O-O-R²structure (2A)

Wherein R is¹And R²Each is an alkyl group.

In one embodiment, R of structure (2A)¹And R²Each is C₁-C₂₀Alkyl or C₁-C₁₀An alkyl group.

Organic peroxides exclude organic hydroperoxides containing-OOH groups.

Organic peroxides excluded from having the formula H₂O₂Hydrogen peroxide of (2) because hydrogen peroxide is devoid of carbon.

The organic peroxide may include two or more embodiments disclosed herein.

iii. phosphine oxide

The compositions of the present invention comprise phosphine oxide.

"phosphine oxides" are compounds having a phosphorus atom bonded to three carbon atoms and a double bond between the phosphorus atom and an oxygen atom.

Examples of suitable phosphine oxides are compounds having the following structure (1):

wherein R is¹、R²And R³Each independently selected from C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Heterohydrocarbyl and combinations thereof;

with the proviso that the phosphorus atom is bound to each R¹、R²And R³To the carbon atom in (b).

In one embodiment, the hydrocarbyl group of structure (1) is C₁-C₂₀A hydrocarbon group, or C₁-C₁₀A hydrocarbon group, or C₂-C₈A hydrocarbon group, or C₆-C₈A hydrocarbyl group. Suitable C₁-C₄₀Examples of hydrocarbyl groups include phenyl, n-octyl, and combinations thereof.

In one embodiment, the heterohydrocarbyl group of structure (1) is C₁-C₂₀Heterohydrocarbyl, or C₁-C₁₀Heterohydrocarbyl, or C₂-C₁₀Heterohydrocarbyl, or C₆-C₁₀A heterohydrocarbyl group. Suitable C₁-C₄₀An example of a heterocarbyl group is 2, 4, 6-trimethylbenzoyl.

In one embodiment, R of structure (1)¹、R²And R³Each independently selected from C₆-C₈Hydrocarbyl radical, C₆-C₁₀Heterohydrocarbyl groups, and combinations thereof.

In one embodiment, R of structure (1)¹、R²And R³Each independently selected from phenyl, n-octyl and 2, 4, 6-trimethylbenzoyl.

In the structure (1)，R¹、R²And R³May be the same or different. In one embodiment, R¹、R²And R³The same is true. In another embodiment, R¹、R²And R³At least two or each of which is different.

In one embodiment, R¹、R²And R³Each is phenyl. The phosphine oxide is triphenylphosphine oxide.

In one embodiment, R¹、R²And R³Each is n-octyl. The phosphine oxide is tris (n-octyl) phosphine oxide.

In one embodiment, R¹And R²Each is phenyl, and R³Is 2, 4, 6-trimethylbenzoyl. The phosphine oxide is diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide.

In one embodiment, R¹And R³Each is 2, 4, 6-trimethylbenzoyl, and R²Is phenyl. The phosphine oxide is phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.

In one embodiment, the phosphine oxide is selected from the group consisting of triphenylphosphine oxide, tris (n-octyl) phosphine oxide, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, and combinations thereof.

The phosphine oxide may comprise two or more embodiments disclosed herein.

Protonic acid source compound

The composition of the invention comprises a protonic acid source compound.

A "protonic acid source compound" (or "PASC") is a protonic acid or protonic acid-generator compound ("PAGC").

A. Protonic acid

A "protonic acid" is one that generates hydrogen ions (H) under polyolefin melt extrusion or other conditions⁺) And is capable of causing ionic decomposition of the organic peroxide rather than radical decomposition. Protic acids exclude polyolefin-based groups. The protic acid may act as a proton donor and may accept a pair of electrons to form a covalent bond.Examples of suitable protic acids include sulfur-based acids, carboxylic acids, phosphorus-based acids, and combinations thereof.

"Sulfur-based acids" are organic acids containing a sulfur atom. Examples of suitable sulfur-based acids include sulfonic acids, sulfenic acids, sulfinic acids, and combinations thereof.

"sulfonic acid" is an organic acid containing a group of the following structure (3):

an example of a suitable sulfonic acid is dodecylbenzene sulfonic acid (DBSA).

"sulfenic acid" is an organic acid containing a group of the following structure (4):

-S-O-H structure (4)

An example of a suitable sulfenic acid is methane sulfinic acid.

"sulfinic acid" is an organic acid containing a group of the following structure (5):

an example of a suitable sulfinic acid is phenylsulfinic acid.

A "phosphorus-based acid" is an organic acid containing a phosphorus atom. Examples of suitable phosphorus-based acids include phosphorous acid, phosphoric acid, and combinations thereof.

In one embodiment, the protic acid is selected from the group consisting of sulfonic acids, sulfenic acids, sulfinic acids, carboxylic acids, and combinations thereof. In another embodiment, the protic acid is selected from the group consisting of sulfonic acids, sulfenic acids, sulfinic acids, and combinations thereof.

The protic acid may comprise two or more embodiments disclosed herein.

B. Protonic acid-generator compounds

A "protic acid-generator compound" (or "PAGC") is a substance that is a non-protic acid, but contains functional groups that react with oxygen and/or oxidation products (such as hydroperoxides) to convert to or generate a protic acid during formation, storage, processing, and/or extrusion of the compositions of the present invention. PAGC is a potential protic acid. During formation (e.g., melt blending), storage, processing, and/or extrusion of the composition, the PAGC undergoes a single reaction or a series of reactions that produce protic acids.

Examples of suitable PAGCs include Antioxidants (AO), additives, fillers, and combinations thereof. Examples of suitable antioxidants include phosphite antioxidants and sulfur-based antioxidants.

In one embodiment, the PAGC is a phosphite antioxidant. Phosphite antioxidants and their oxidation products (phosphates) undergo hydrolysis to produce phosphorus-based acids in use (as antioxidants) and/or during processing. Oxidation may occur before or after hydrolysis. An example of a suitable phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite, available as IRGAFOS from BASF Inc^TM168 commercially available.

In one embodiment, PAGC is a sulfur-based antioxidant. The sulfur-based antioxidant is oxidized during formation, storage, processing, and/or extrusion of the inventive composition. The oxidation product undergoes thermal cracking to form a sulfur-based acid, such as a sulfonic acid, a sulfenic acid, a sulfinic acid, and combinations thereof. The sulfur-based acid may undergo further oxidation to form a sulfur-based acid having a higher oxidation state. Examples of sulfur-based antioxidants include distearylthiodipropionate (DSTDP); 4, 4' -Thiobis (2-tert-butyl-5-methylphenol) (e.g., LOWINOX^TMTBM-6, available from Addivant Corporation); 2, 2' -Thiobis (6-tert-butyl-4-methylphenol) (e.g., LOWINOX^TMTBP-6, available from Addivant Corporation); and combinations thereof.

In one embodiment, PAGC is an ester additive. The ester may hydrolyze during use, processing, and/or storage to form a carboxylic acid. Examples of suitable ester additives include pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (e.g., IRGANOX)^TM1010, available from basf); octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionate (e.g., IRGANOX)^TM1076, available from Ciba Inc. (Ciba Inc.), and combinations thereof.

In one embodiment, the PAGC is selected from the group consisting of sulfur-based antioxidants, phosphite antioxidants, ester additives, and combinations thereof.

In one embodiment, the PAGC is selected from the group consisting of sulfur-based antioxidants, phosphite antioxidants, and combinations thereof.

A PAGC may include two or more embodiments disclosed herein.

The compositions of the present invention may comprise a PAGC (e.g., a sulfur-based antioxidant) when the composition is formed, and once the PAGC undergoes a reaction (e.g., oxidation) that produces a protic acid (e.g., a sulfonic acid, a sulfenic acid, and/or a sulfinic acid), it will comprise a protic acid. At a single time point, the composition may comprise (i) only PAGC (and not protic acid), (ii) a combination of both PAGC and protic acid, or (iii) only protic acid (and not PAGC).

PASCs and further PAGCs are distinct from ethylene-based polymers. In other words, PASC and further PAGC exclude ethylene-based polymers and any oxidation reaction products from ethylene-based polymers.

The PASC may include two or more embodiments disclosed herein.

v. optional additives

The compositions of the present invention may comprise one or more additives. Examples of suitable additives include antioxidants, colorants, corrosion inhibitors, lubricants, Ultraviolet (UV) absorbers or stabilizers, antiblocking agents, coupling agents, compatibilizers, plasticizers, fillers, processing aids, moisture scavengers, scorch retarders, metal deactivators, and combinations thereof.

The additive may comprise two or more of the embodiments disclosed herein.

Composition (vi)

The composition of the present invention comprises: (i) an ethylene-based polymer; (ii) an organic peroxide; (iii) a phosphine oxide; (iv) PASC selected from the group consisting of protic acids, PAGC, and combinations thereof; and (v) optionally additives.

In one embodiment, the composition comprises: (i) an ethylene-based polymer; (ii) an organic peroxide; (iii) phosphine oxides having the structure (1)

Wherein R is¹、R²And R³Each independently selected from C₁-C₄₀Hydrocarbyl radical, C₁-C₄₀Heterohydrocarbyl and combinations thereof; with the proviso that the phosphorus atom is bound to each R¹、R²And R³The carbon atom in (1) is bonded; (iv) PASC selected from the group consisting of protic acids, PAGC, and combinations thereof; and (v) optionally additives.

In one embodiment, the composition comprises 45 wt%, or 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt% to 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 98 wt%, or 99 wt%, or 99.96 wt% of the ethylene-based polymer, based on the total weight of the composition.

In one embodiment, the composition comprises 0.02 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1 wt% to 2 wt%, or 3 wt%, or 4 wt%, or 5 wt% of the organic peroxide, based on the total weight of the composition.

In one embodiment, the composition comprises 0.001 wt%, or 0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.02 wt%, or 0.04 wt%, or 0.05 wt% to 0.10 wt%, or 0.20 wt%, or 0.30 wt%, or 0.40 wt%, or 0.50 wt%, or 0.60 wt%, or 0.70 wt%, or 0.80 wt%, or 0.90 wt%, or 1.00 wt% phosphine oxide, based on the total weight of the composition. In one embodiment, the composition comprises from 0.001 wt% to 1.00 wt%, or from 0.01 wt% to 0.50 wt%, or from 0.01 wt% to 0.10 wt%, or from 0.02 wt% to 1.00 wt%, or from 0.02 wt% to 0.60 wt%, or from 0.04 wt% to 0.60 wt% phosphine oxide, based on the total weight of the composition.

In one embodiment, the composition comprises 0.001 mole%, or 0.01 mole%, or 0.02 mole%, or 0.04 mole%, or 0.1 mole% to 0.4 mole%, or 0.5 mole%, or 1.0 mole%, or 2.0 mole%, or 5.0 mole%, or 10 mole%, or 15 mole%, or 20 mole%, or 25 mole% of the phosphine oxide, based on the total composition.

In one embodiment, the composition comprises 0.0001 wt%, or 0.001 wt%, or 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 5 wt%, or 10 wt%, or 15 wt% to 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%, or 50 wt% PASC, based on the total weight of the composition.

In one embodiment, the composition comprises 0 wt%, or greater than 0 wt%, or 0.001 wt%, or 0.002 wt%, or 0.005 wt%, or 0.006 wt% to 0.007 wt%, or 0.008 wt%, or 0.009 wt%, or 0.01 wt%, or 0.1 wt%, or 0.2 wt%, or 0.3 wt%, or 0.4 wt%, or 0.5 wt%, or 1.0 wt%, or 2.0 wt%, or 2.5 wt%, or 3.0 wt%, or 4.0 wt%, or 5.0 wt% to 6.0 wt%, or 7.0 wt%, or 8.0 wt%, or 9.0 wt%, or 10.0 wt%, or 15.0 wt%, or 20.0 wt% of the additive, based on the total weight of the composition.

In one embodiment, the composition has a retained peroxide percentage of 2%, or 5%, or 7%, or 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 2 hours. In another embodiment, the composition has a retained peroxide percentage of 2% to 100%, or 5% to 100%, or 10% to 100%, or 15% to 100%, or 20% to 100%, or 50% to 100%, or 70% to 100%, or 75% to 100%, or 90% to 100%, or 95% to 100%, or 98% to 100% after heating at 100 ℃ for 2 hours. Without wishing to be bound by any particular theory, it is believed that the inclusion of the phosphine oxide in the compositions of the present invention prevents or slows the decomposition of the organic peroxide, which is typically caused by the presence of protic acids in the composition. By stopping or slowing the decomposition of the organic peroxide during the formation, storage, processing, and/or extrusion of the inventive composition, the phosphine oxide is advantageously capable of retaining the organic peroxide such that the organic peroxide is present and can be used for free radical crosslinking after extrusion of the inventive composition onto a conductor. When there is insufficient retention of the organic peroxide during formation, storage, processing, and/or extrusion of the inventive composition, the coating formed from the inventive composition does not crosslink after extrusion onto the conductor.

In one embodiment, the composition has a retained peroxide percentage of 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 1.5 hours.

In one embodiment, the composition has a retained peroxide percentage of 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 1.0 hour.

In one embodiment, the composition has a percent retained peroxide of 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 0.5 hours.

In one embodiment, the composition comprises, based on the total weight of the composition: (i)45 wt%, or 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt% to 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 98 wt%, or 99 wt%, or 99.96 wt% of an ethylene-based polymer; (ii)0.02 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1 wt% to 2 wt%, or 3 wt%, or 4 wt%, or 5 wt% of an organic peroxide; (iii)0.001 wt%, or 0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.02 wt%, or 0.04 wt%, or 0.05 wt% to 0.10 wt%, or 0.20 wt%, or 0.30 wt%, or 0.40 wt%, or 0.50 wt%, or 0.60 wt%, or 0.70 wt%, or 0.80 wt%, or 0.90 wt%, or 1.00 wt% of phosphine oxide; (iv)0.0001 wt%, or 0.001 wt%, or 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 5 wt%, or 10 wt%, or 15 wt% to 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%, or 50 wt% of PASC; (v)0 wt%, or greater than 0 wt%, or 0.001 wt%, 0.005 wt%, or 0.01 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 2.0 wt%, or 3.0 wt%, or 4.0 wt%, or 5.0 wt% to 6.0 wt%, or 7.0 wt%, or 8.0 wt%, or 9.0 wt%, or 10.0 wt%, or 15.0 wt%, or 20.0 wt% of an additive; and the composition has one, some or all of the following properties: (a) a retained peroxide percentage of 2%, or 5%, or 7%, or 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 2 hours; and/or (b) a percentage of peroxide retained after heating at 100 ℃ for 1.5 hours of from 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100%: and/or (c) a percentage retained peroxide of 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 1.0 hour; and/or (d) a percentage of peroxide retained after heating at 100 ℃ for 0.5 hour of 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100%.

In one embodiment, the composition comprises, based on the total weight of the composition: (i)45 wt%, or 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt% to 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 98 wt%, or 99 wt%, or 99.96 wt% of an ethylene-based polymer; (ii)0.02 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1 wt% to 2 wt%, or 3 wt%, or 4 wt%, or 5 wt% of an organic peroxide; (iii)0.001 wt%, or 0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.02 wt%, or 0.04 wt%, or 0.05 wt% to 0.10 wt%, or 0.20 wt%, or 0.30 wt%, or 0.40 wt%, or 0.50 wt%, or 0.60 wt%, or 0.70 wt%, or 0.80 wt%, or 0.90 wt%, or 1.00 wt% of phosphine oxide; (iv)0.0001 wt%, or 0.001 wt%, or 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 5 wt%, or 10 wt%, or 15 wt% to 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%, or 50 wt% of PASC selected from the group consisting of sulfonic acid, sulfenic acid, sulfinic acid, sulfur-based antioxidants, and combinations thereof; (v)0 wt%, or greater than 0 wt%, or 0.001 wt%, 0.005 wt%, or 0.01 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 2.0 wt%, or 3.0 wt%, or 4.0 wt%, or 5.0 wt% to 6.0 wt%, or 7.0 wt%, or 8.0 wt%, or 9.0 wt%, or 10.0 wt%, or 15.0 wt%, or 20.0 wt% of an additive; and the composition has one, some or all of the following properties: (a) a retained peroxide percentage of 2%, or 5%, or 7%, or 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 2 hours; and/or (b) a percentage retained peroxide of 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 1.5 hours; and/or (c) a percentage retained peroxide of 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 1.0 hour; and/or (d) a percentage of peroxide retained after heating at 100 ℃ for 0.5 hour of 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100%.

In one embodiment, the composition contains 0.001 wt%, or 0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.02 wt%, or 0.04 wt%, or 0.10 wt% to 0.60 wt%, or 1.0 wt% phosphine oxide, based on the total weight of the composition, and R of structure (1)¹、R²And R³Each is phenyl. In one embodiment, the composition has a retained peroxide percentage of 2%, or 5%, or 7%, or 10%, or 20%, or 50%, or 55%, or 70%, or 80%, or 90%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100 ℃ for 2 hours.

In one embodiment, the composition contains 0.001 wt.%, or 0.003 wt.%, or 0.005 wt.%, or 0.007 wt.%, or 0.01 wt.%, or 0.05 wt.%, or 0.10 wt.% to 1.0 wt.% phosphine oxide, based on the total weight of the composition, and R is¹、R²And R³Each is n-octyl. In one embodiment, the composition has a percent retained peroxide of 70%, or 80%, or 90%, or 94%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100 ℃ for 2 hours.

In one embodiment, the composition contains 0.001 wt%, or 0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.05 wt%, or 0.10 wt% to 1.0 wt% of phosphine oxide, R, based on the total weight of the composition¹And R²Each is phenyl, and R³Is 2, 4, 6-trimethylbenzoyl. In one embodiment, the composition has a percent retained peroxide of 70%, or 75%, or 80%, or 90% to 100% after heating at 100 ℃ for 2 hours.

In one embodiment, the composition contains 0.001 wt%, or 0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.05 wt%, or 0.10 wt% to 1.0 wt% of phosphine oxide, R, based on the total weight of the composition¹And R³Each is 2, 4, 6-trimethylbenzoyl, and R²Is phenyl. In one embodiment, the composition has a percent retained peroxide of 50%, or 60%, or 70%, or 75%, or 76% to 100% after heating at 100 ℃ for 2 hours.

In one embodiment, the composition comprises, based on the total weight of the composition:

(i)45 wt%, or 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt% to 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 97 wt%, or 98 wt%, or 99 wt% of an ethylene-based polymer;

(ii)0.02 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1 wt% to 2 wt%, or 3 wt%, or 4 wt%, or 5 wt% of an organic peroxide;

(iii)0.001 wt%, or 0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.2 wt%, or 0.3 wt%, or 0.4 wt%, or 0.5 wt% to 0.6 wt%, or 0.7 wt%, or 0.8 wt%, or 0.9 wt%, or 1.0 wt% of phosphine oxide;

(iv)0.0001 wt%, or 0.001 wt%, or 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 5 wt%, or 10 wt%, or 15 wt% to 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%, or 50 wt% of PASC, which is PAGC;

(v) 0%, or greater than 0%, or 0.001%, 0.005%, or 0.01%, or 0.1%, or 0.5%, or 1.0%, or 2.0%, or 3.0%, or 4.0%, or 5.0% to 6.0%, or 7.0%, or 8.0%, or 9.0%, or 10.0%, or 15.0%, or 20.0% by weight of an additive, wherein the total amount of components (i) - (v) is 100% by weight; and the composition has:

(a) after 21 days of heating at 70 ℃, 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% of the MH remained.

In one embodiment, the composition comprises, based on the total weight of the composition:

(i)95 wt%, or 96 wt%, or 97 wt% to 98 wt%, or 99 wt% of an ethylene-based polymer;

(ii)0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1 wt% to 2 wt%, or 3 wt%, or 4 wt%, or 5 wt% of an organic peroxide;

(iii)0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.2 wt%, or 0.3 wt%, or 0.4 wt%, or 0.5 wt% to 0.6 wt%, or 0.7 wt% phosphine oxide;

(iv)0.1 wt%, or 0.2 wt%, or 0.25 wt% to 0.3 wt%, or 0.4 wt%, or 0.5 wt% PAGC;

(v)0 wt%, or greater than 0 wt%, or 0.001 wt%, 0.005 wt%, or 0.01 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt% of an additive, wherein the total amount of components (i) - (v) is 100 wt%; and the composition has:

(a) after 21 days of heating at 70 ℃, 95%, or 97% to 98%, or 99%, or 100% of the remaining MH (hereinafter composition 1).

In one embodiment, composition 1 has all of the above characteristics set forth in the preceding paragraph and the PAGC of composition 1 is a sulfur-based antioxidant. In another embodiment, the sulfur-based antioxidant of composition 1 is distearylthiodipropionate (DSTDP).

Without wishing to be bound by any particular theory, it is believed that the inclusion of the phosphine oxide in the compositions of the present invention prevents or slows the ionic decomposition of the organic peroxide, which is typically caused by the presence of PASCs (and especially PAGCs) in the composition. By stopping or slowing the ionic decomposition of the organic peroxide during the formation, storage, processing, and/or extrusion of the inventive composition, the phosphine oxide is advantageously capable of retaining the organic peroxide so that the organic peroxide is present and can be used for free radical crosslinking after the inventive composition is extruded onto a conductor. When there is insufficient retention of the organic peroxide during formation, storage, processing, and/or extrusion of the inventive composition, the coating formed from the inventive composition does not crosslink after extrusion onto the conductor.

The sum of the components in each of the compositions disclosed herein (including the aforementioned compositions) yields 100 weight percent (wt%).

The composition may be formed by melt blending (e.g., by extrusion) all or some of the components. In one embodiment, the ethylene-based polymer, phosphine oxide, PASC, and optional additives are extruded and pelletized. Then, the organic peroxide is absorbed into the pellets in the soaking step. The pellets containing all components may be stored in bags, drums, boxes or rail cars for a period of time. The pellets may be added to an extruder and extruded onto the conductor surface.

In an alternative embodiment, all of the components of the composition are combined in an extruder and the composition is extruded onto the conductor surface.

The composition may comprise two or more embodiments disclosed herein.

In one embodiment, the composition is crosslinked.

The composition may comprise two or more embodiments disclosed herein.

The present invention also provides a crosslinked product prepared by heating a composition to a temperature sufficient to crosslink the composition. The crosslinked product may be a coating on a conductor.

Coated conductor

The invention also provides a coated conductor. The coated conductor comprises a conductor and a coating on the conductor, the coating comprising a composition. The composition comprises: (i) an ethylene-based polymer; (ii) an organic peroxide; (iii) a phosphine oxide; (iv) PASC selected from the group consisting of protic acids, PAGC, and combinations thereof; and (v) optionally additives.

In one embodiment, a coated conductor comprises a conductor and a coating on the conductor, the coating comprising a composition. The composition comprises: (i) an ethylene-based polymer; (ii) an organic peroxide; (iii) phosphine oxides having the structure (1) as defined above; (iv) PASC selected from the group consisting of protic acids, PAGC, and combinations thereof; and (v) optionally additives.

The composition, ethylene-based polymer, organic peroxide, phosphine oxide, PASC, and optional additive can be any of the corresponding ethylene-based polymers, organic peroxides, phosphine oxides, PASCs, and optional additives disclosed herein.

In one embodiment, the coating comprises a composition having a percentage of retained peroxide of 2%, or 5%, or 7%, or 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 2 hours. In another embodiment, the coating comprises a composition having a percentage retained peroxide of 2% to 100%, or 5% to 100%, or 10% to 100%, or 15% to 100%, or 20% to 100%, or 50% to 100%, or 70% to 100%, or 80% to 100%, or 90% to 100% after heating at 100 ℃ for 2 hours. Without wishing to be bound by any particular theory, it is believed that the inclusion of the phosphine oxide in the composition prevents or slows the ionic decomposition of the organic peroxide, which is typically caused by the presence of protic acids in the composition. By stopping or slowing the ionic decomposition of the organic peroxide during the formation, storage, processing, and/or extrusion of the composition, the phosphine oxide advantageously is capable of retaining the organic peroxide so that the organic peroxide is present and available for free radical crosslinking after the inventive composition is extruded onto a conductor. When there is insufficient retention of the organic peroxide during formation, storage, processing, and/or extrusion of the inventive composition, the coating formed from the inventive composition does not crosslink after extrusion onto the conductor.

In one embodiment, the coating comprises a composition having a retained peroxide percentage of 5%, or 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 1.5 hours.

In one embodiment, the coating comprises a composition having a retained peroxide percentage of 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 1.0 hour.

In one embodiment, the coating comprises a composition having a percent retained peroxide of 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 0.5 hours.

In one embodiment, the coating is an insulating sheath for the conductor. In another embodiment, the coating is a jacket for a conductor.

A method of producing a coated conductor comprises heating the inventive composition to at least the melting temperature of the ethylene-based polymer, and then extruding the polymer melt blend onto the conductor. The term "onto … …" includes direct contact or indirect contact between the polymer melt blend and the conductor. The polymer melt blend is in an extrudable state.

The coating is on the conductor. The coating may be one or more internal layers, such as an insulating layer. The coating may completely or partially cover or otherwise surround or encase the conductor. The coating may be the only component surrounding the conductor. When the coating is the only component surrounding the conductor, the coating may act as a jacket and/or an insulator. In one embodiment, the coating is the outermost layer on the coated conductor. Alternatively, the coating may be one layer of a multi-layer sheath or sheath that encases the metallic conductor. In one embodiment, the coating directly contacts the conductor. In another embodiment, the coating directly contacts the insulating layer surrounding the conductor.

In one embodiment, the coating directly contacts the conductor. As used herein, the term "direct contact" is a coating configuration in which the coating is positioned proximate to the conductor, the coating contacts the conductor, and there are no intervening layers, no intervening coatings, and/or no intervening structures between the coating and the conductor.

In another embodiment, the coating indirectly contacts the conductor. As used herein, the term "indirect contact" is a coating configuration in which there is an intervening layer, intervening coating, or intervening structure between the coating and the conductor. Examples of suitable intervening layers, intervening coatings, and intervening structures include insulating layers, moisture barriers, buffer tubes, and combinations thereof. Examples of suitable insulating layers include foamed insulating layers, thermoplastic insulating layers, crosslinked insulating layers, and combinations thereof.

In one embodiment, the coating is an insulation layer of a high voltage power transmission cable or an ultra high voltage power transmission cable.

The coating is crosslinked. In one embodiment, crosslinking of the composition of the invention begins in the extruder, but only to a minimal extent. In another embodiment, crosslinking is delayed until the composition is extruded on the conductor. Crosslinking of the compositions of the present invention may be initiated and/or accelerated by the application of heat or radiation. In one embodiment, after extrusion, the coated conductor is conditioned in a continuous vulcanization tube at a temperature of 160 ℃, or 180 ℃ to 200 ℃, or 400 ℃.

In one embodiment, the coated conductor comprises, consists essentially of, or consists of: a conductor and a coating on the conductor. The coating comprises, consists essentially of, or consists of: a composition is provided. The composition comprises, consists essentially of, or consists of the following, based on the total weight of the composition: (i)45 wt%, or 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt% to 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 98 wt%, or 99 wt%, or 99.96 wt% of an ethylene-based polymer; (ii)0.02 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1 wt% to 2 wt%, or 3 wt%, or 4 wt%, or 5 wt% of an organic peroxide; (iii)0.001 wt%, or 0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.02 wt%, or 0.04 wt%, or 0.05 wt% to 0.10 wt%, or 0.20 wt%, or 0.30 wt%, or 0.40 wt%, or 0.50 wt%, or 0.60 wt%, or 0.70 wt%, or 0.80 wt%, or 0.90 wt%, or 1.00 wt% of phosphine oxide; (iv)0.0001 wt%, or 0.001 wt%, or 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 5 wt%, or 10 wt%, or 15 wt% to 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%, or 50 wt% of PASC; (v) 0%, or greater than 0%, or 0.001%, 0.005%, or 0.01%, or 0.1%, or 0.5%, or 1.0%, or 2.0%, or 3.0%, or 4.0%, or 5.0% to 6.0%, or 7.0%, or 8.0%, or 9.0%, or 10.0%, or 15.0%, or 20.0% by weight of an additive; and the composition has one, some or all of the following properties: (a) a retained peroxide percentage of 2%, or 5%, or 7%, or 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 2 hours; and/or (b) a percentage of retained peroxide of 5%, or 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 1.5 hours; and/or (c) a retained peroxide percentage of 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 1.0 hour; and/or (d) a percentage of peroxide retained after heating at 100 ℃ for 0.5 hour of 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100%.

In one embodiment, the coated conductor comprises, consists essentially of, or consists of: a conductor and a coating on the conductor. The coating comprises, consists essentially of, or consists of: a composition is provided. The composition comprises, consists essentially of, or consists of the following, based on the total weight of the composition: (i)45 wt%, or 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt% to 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 98 wt%, or 99 wt%, or 99.96 wt% of an ethylene-based polymer; (ii)0.02 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1 wt% to 2 wt%, or 3 wt%, or 4 wt%, or 5 wt% of an organic peroxide; (iii)0.001 wt%, or 0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.02 wt%, or 0.04 wt%, or 0.05 wt% to 0.10 wt%, or 0.20 wt%, or 0.30 wt%, or 0.40 wt%, or 0.50 wt%, or 0.60 wt%, or 0.70 wt%, or 0.80 wt%, or 0.90 wt%, or 1.00 wt% of phosphine oxide; (iv)0.0001 wt%, or 0.001 wt%, or 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 5 wt%, or 10 wt%, or 15 wt% to 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%, or 50 wt% of PASC selected from the group consisting of sulfonic acid, sulfenic acid, sulfinic acid, sulfur-based antioxidants, and combinations thereof: (v)0 wt%, or greater than 0 wt%, or 0.001 wt%, 0.005 wt%, or 0.01 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 2.0 wt%, or based on 3.0 wt%, or 4.0 wt%, or 5.0 wt% to 6.0 wt%, or 7.0 wt%, or 8.0 wt%, or 9.0 wt%, or 10.0 wt%, or 15.0 wt%, or 20.0 wt% of an additive; and the composition has one, some or all of the following properties: (a) a retained peroxide percentage of 2%, or 5%, or 7%, or 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 2 hours; and/or (b) a percentage of retained peroxide of 5%, or 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 1.5 hours; and/or (c) a retained peroxide percentage of 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100 ℃ for 1.0 hour; and/or (d) a percentage of peroxide retained after heating at 100 ℃ for 0.5 hour of 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100%.

In one embodiment, the coating comprises a composition comprising 0.001 wt.%, or 0.003 wt.%, or 0.005 wt.%, or 0.007 wt.%, or 0.01 wt.%, or 0.02 wt.%, or 0.04 wt.%, or 0.10 wt.% to 0.60 wt.% or 1.0 wt.% phosphine oxide, based on the total weight of the composition, and R of structure (1)¹、R²And R³Each is phenyl. In one embodiment, the composition has a retained peroxide percentage of 2%, or 5%, or 7%, or 10%, or 15%, or 20%, or 50%, or 55%, or 70%, or 80%, or 90%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100 ℃ for 2 hours.

In one embodiment, the coating comprises a composition comprising 0.001 wt.%, or 0.003 wt.%, or 0.005 wt.%, or 0.007 wt.%, or 0.01 wt.%, or 0.05 wt.%, or 0.10 wt.% to 1.0 wt.% phosphine oxide, based on the total weight of the composition, and R is¹、R²And R³Each is n-octyl. In one embodiment, the composition has a percent retained peroxide of 70%, or 80%, or 90%, or 94%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100 ℃ for 2 hours.

In one embodiment, the coating comprises a composition comprising 0.001 wt.%, or 0.003 wt.%, or 0.005 wt.%, or 0.007 wt.%, or 0.01 wt.%, or 0.05 wt.%, or 0.10 wt.% to 1.0 wt.% of the phosphine oxide, based on the total weight of the composition, R¹And R²Each is phenyl, and R³Is 2, 4, 6-trimethylbenzoyl. In one embodiment, the composition has a percent retained peroxide of 70%, or 75%, or 80%, or 90% to 100% after heating at 100 ℃ for 2 hours.

In one embodiment, the coating comprises a composition comprising 0.001 wt%, or 0.003 wt%, or 0.005 wt%, or 0.007 wt%, or0.01 wt.%, or 0.05 wt.%, or 0.10 wt.% to 1.0 wt.% of a composition of phosphine oxides, R¹And R³Each is 2, 4, 6-trimethylbenzoyl, and R²Is phenyl. In one embodiment, the composition has a percent retained peroxide of 50%, or 60%, or 70%, or 75%, or 76% to 100% after heating at 100 ℃ for 2 hours.

In one embodiment, the coated conductor comprises a conductor and a coating on the conductor. The coating comprises a composition comprising, based on the total weight of the composition:

(i)45 wt%, or 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt% to 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 97 wt%, or 98 wt%, or 99 wt% of an ethylene-based polymer;

(ii)0.02 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1 wt% to 2 wt%, or 3 wt%, or 4 wt%, or 5 wt% of an organic peroxide;

(iii)0.001 wt%, or 0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.2 wt%, or 0.3 wt%, or 0.4 wt%, or 0.5 wt% to 0.6 wt%, or 0.7 wt%, or 0.8 wt%, or 0.9 wt%, or 1.0 wt% of phosphine oxide;

(iv)0.0001 wt%, or 0.001 wt%, or 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt%, or 5 wt%, or 10 wt%, or 15 wt% to 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%, or 50 wt% of PASC, which is PAGC;

(v) 0%, or greater than 0%, or 0.001%, 0.005%, or 0.01%, or 0.1%, or 0.5%, or 1.0%, or 2.0%, or 3.0%, or 4.0%, or 5.0% to 6.0%, or 7.0%, or 8.0%, or 9.0%, or 10.0%, or 15.0%, or 20.0% by weight of an additive, wherein the total amount of components (i) - (v) is 100% by weight; and the composition has:

(a) after 21 days of heating at 70 ℃, 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% of the MH remained.

In one embodiment, the coating on the conductor comprises a composition comprising:

(i)95 wt%, or 96 wt%, or 97 wt% to 98 wt%, or 99 wt% of an ethylene-based polymer;

(ii)0.05 wt%, or 0.1 wt%, or 0.5 wt%, or 1 wt% to 2 wt%, or 3 wt%, or 4 wt%, or 5 wt% of an organic peroxide;

(iii)0.003 wt%, or 0.005 wt%, or 0.007 wt%, or 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.2 wt%, or 0.3 wt%, or 0.4 wt%, or 0.5 wt% to 0.6 wt%, or 0.7 wt% phosphine oxide;

(iv)0.1 wt%, or 0.2 wt%, or 0.25 wt% to 0.3 wt%, or 0.4 wt%, or 0.5 wt% PAGC;

(v)0 wt%, or greater than 0 wt%, or 0.001 wt%, 0.005 wt%, or 0.01 wt%, or 0.1 wt%, or 0.5 wt%, or 1.0 wt% of an additive, based on the total weight of the composition, wherein the total amount of components (i) - (v) is 100 wt%; and the composition has:

(a) after 21 days of heating at 70 ℃, 95%, or 97% to 98%, or 99%, or 100% of the remaining MH (hereinafter composition 1).

In one embodiment, composition 1 has all of the above characteristics set forth in the preceding paragraph and the PAGC of composition 1 is a sulfur-based antioxidant. In another embodiment, the sulfur-based antioxidant of composition 1 is distearylthiodipropionate (DSTDP).

In one embodiment, the coated conductor is selected from the group consisting of fiber optic cables, communication cables (such as telephone cables or Local Area Network (LAN) cables), power cables, wiring for consumer electronics, power cables, power charger wires for cellular telephones and/or computers, computer data wires, power cords, appliance wiring materials, home wiring materials, consumer electronics accessory wires, and any combination thereof.

In another embodiment, the present compositions are melt-formed into articles other than coatings on conductors (e.g., electrical connectors or components of electrical connectors).

The coated conductor may include two or more embodiments disclosed herein.

By way of example and not limitation, some embodiments of the invention will now be described in detail in the following examples.

Examples of the invention

The materials used in the examples are provided in table 1 below.

TABLE 1 materials

The following three types of stock solutions were prepared and used to make sample solutions: (i) dicumyl peroxide (DCP) solution in dodecane at 0.1154M (stock solution a); (ii) dodecylbenzene sulfonic acid (DBSA) solution in dodecane under 0.00346M (stock solution B); and (iii) a solution of 0.1154M DCP in dodecane containing 0.1% by weight of phosphine oxide (stock solution C). Stock solution C was stirred (1-2 minutes) in an oil bath set at 80 ℃ to ensure complete dissolution of the phosphine oxide.

The sample and comparative solutions were formed in 6 dram glass vials. Dodecane mimics the properties of ethylene-based polymers (that is, serves as a model). The solution was stirred with a magnetic stir bar. The composition of each solution is provided in table 2 below.

Comparative solution 1(CS 1) was prepared by adding 2mL of stock solution a and 2mL of stock solution B to a glass vial and mixing with a magnetic stir bar at room temperature. The total volume of CS 1 was 4 mL. CS 1 contains 0.0577M DCP (equivalent to 2 wt% DCP) with 0.00173M DBSA. CS 1 does not contain phosphine oxide. The composition of CS 1 is provided in table 2 below.

Comparative solution 2(CS 2) was prepared by adding 2mL of stock solution a and 2mL of dodecane to a glass vial and mixing with a magnetic stir bar at room temperature. The total volume of CS 2 was 4 mL. CS 2 contained 0.0577M DCP (equivalent to 2 wt% DCP). CS 2 contains no phosphine oxide and no DBSA. The composition of CS 2 is provided in table 2 below.

Each sample solution 1-5 was prepared by adding 2mL of stock solution B, XmL stock solution C, and (2-X) mL of stock solution a to a glass vial and mixing with a magnetic stir bar at room temperature, where X equals 10 times the weight percent concentration of phosphine oxide. For example, to prepare a sample solution containing 0.05 wt.% phosphine oxide, 2mL of stock solution B was mixed with 1.5mL of stock solution a and 0.5mL of stock solution C. The compositions of sample solutions 1-5 are provided in table 2 below.

Each sample solution 6-10 was prepared by adding 2mL of stock solution a and 2mL of stock solution B to a glass vial and mixing with a magnetic stir bar at room temperature. Phosphine oxide was added to the contents of the glass vial. Sample solutions 9 and 10 were prepared in amber 6 dram glass vials. The compositions of sample solutions 6-10 are provided in table 2 below.

Then, the glass vial was immersed in Corning^TMPC-420D stirring hot plate in a well stirred (500rpm) silicon oil bath maintained at a temperature of 100 ℃. The comparative solution and the sample solution were each heated to a temperature of 100 ℃ and maintained at 100 ℃ while mixing, and 600 μ l aliquots were taken after 2 minutes (at which time phosphine oxide was completely dissolved in the solution), 0.5 hours, 1.0 hours, 1.5 hours, and 2.0 hours of time. The comparison solution and the sample solution were heated in a glass vial without a cap or cover (in other words, the sample solution was exposed to the atmosphere while being heated).

Each 600. mu.l aliquot taken from the glass vial was placed in a 1.5mL microcentrifuge tube, cooled in an ice bath for 7-10 minutes, and centrifuged at 6,000rpm in a VWR Galaxy microcentrifuge, model C1413. Then, 350. mu.l of a clear fraction was taken from each aliquot and combined with 700. mu.l of isopropanol and analyzed by liquid chromatography to determine the concentration of DCP present in the fraction (Shimadzu LC-20AD liquid chromatography with an SPD-20A UV visible detector set at 210 nm; the column was a Waters SunAire C182.1mm. times.50 mm column with a particle size of 3.5 μm; the mobile phase at a flow rate of 0.25 ml/min was 75% methanol/25% water). The amount of DCP in the sample solution measured after 2 minutes at 100 ℃ was referred to as the initial DCP amount.

The percentage of dicumyl peroxide (DCP) retained was calculated according to the following equation (1A):

wherein t is 0.5 hour, 1.0 hour, 1.5 hours, or 2.0 hours.

For example, after heating at 100 ℃ for 2 hours, solution 1 contains 0.1631 wt% DCP. The initial amount of DCP in solution 1 (i.e., after 2 minutes at 100 ℃) was 2.0854 wt%. Thus, the percentage of DCP retained by solution 1 after 2 hours of heating at 100 ℃ was calculated according to the following equation (1B):

the percentage of DCP retained by solution 1 after heating at 100 ℃ for 2 hours was 7.82%.

The properties of the sample solution and the comparative solution are provided in table 2 below.

TABLE 2

CS 1 is a comparative solution containing: (i) dodecane (to simulate an ethylene-based polymer); (ii) dicumyl peroxide (DCP); and (iii) dodecylbenzene sulfonic acid (DBSA) -and no phosphine oxide. As shown in table 2, CS 1 showed a percentage of peroxide (here DCP) retained of only 0.44% after heating at 100 ℃ for 2 hours. Thus, CS 1 does not retain the organic peroxide at a suitable concentration after heating at 100 ℃ for 2 hours to crosslink the composition. Thus, CS 1 represents a peroxide-containing polymer composition that is not suitable for wire and cable applications, as well as other applications.

CS 2 is a comparative composition comprising: (i) dodecane (to mimic the ethylene-based polymer) and (ii) dicumyl peroxide (DCP) -and is free of phosphine oxide or DBSA. Thus, CS 2 lacks the Protic Acid Source Compound (PASC) that causes the ionic dissociation of DCP.

The applicant has surprisingly found a composition (solutions 1-10) comprising: (i) dodecane (to simulate an ethylene-based polymer); (ii) dicumyl peroxide (DCP); (iii) phosphine oxides (triphenylphosphine oxide, tris (n-octyl) phosphine oxide, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide or phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide); and (iv) dodecylbenzene sulfonic acid (DBSA), which composition advantageously exhibits a peroxide (here DCP) retention percentage of greater than 7%, and in some cases greater than 70%, after heating for 2 hours at 100 ℃. Thus, solutions 1-10 represent peroxide-containing polymer compositions suitable for wire and cable applications, as well as other applications.

Ethylene-based polymer compositions

Using a cam rotor, 420mL of Brabender was used at 180 ℃ and 30 revolutions per minute (rpm)^TMThe mixing bowl prepared a masterbatch of additive-containing ethylene-based polymer (low density polyethylene; LDPE; 0.921g/cc, 2g/10min melt index, measured at 190 ℃ and 2.16kg load) for a total mixing time of 5 minutes from the loading time. The composition of each Masterbatch (MB) is shown in table 3 below.

Table 3: master batch

A "solid" mixture of ingredients was made in a vessel, and this "solid" was then loaded into a Brabender mixing bowl and melt mixed to make MB. The molten polymer is taken out of the mixing bowl, flattened into solid form in a cold press, cut into small strips using a guillotine-type slicer andfollowed by using BERLYN^TMThe granulator granulates into small pieces. Feeding the mini-pellets into a Brabender operated by a conventional screw conveyor at 40rpm^TMIn a single screw extruder, where all zones and the set barrel temperature of the head/die were 130 ℃. Using BERLYN^TMThe granulator cuts the resulting polymer strand into uniform pellets to prepare pellets of MB.

Next, the masterbatch was melt mixed with the same LDPE as mentioned above in the proportions shown in table 4 using a twin screw extruder at 60rpm with all zones set to 120 ℃ (resulting in a melt temperature of about 140 ℃) and a 60 mesh screen combination to prepare a strand of pellets that was converted into the "intermediate" compound.

Table 4: "intermediate" compounds

Next, 1.8g of organic peroxide was immersed in 98.2g of each "intermediate" compound to prepare "fully formulated" compounds of the compositions shown in table 5. In the compounds 1 to 5 of the present invention, DSTDP acts as PAGC.

Table 5: "fully formulated" compounds and MH after prolonged storage at 70 ℃

In table 5 above, the percentage of retained MH was calculated according to the following equation (2):

where t is at 70 ℃ for 21 days.

As an example, the percentage retained MH of compound 1 of the present invention was calculated according to the following equation (2A):

(Retention after 21 days)

The retained MH% of compound 1 of the invention is 100%.

After 21 days of aging at 70 ℃, fully formulated compounds 1, 2, 3 and 4 each exhibited a retained MH of 100%.

Without being bound by a particular theory, it is believed that the oxidation by-products of DSTDP form acidic species that can cause non-productive, non-free radical decomposition of the peroxide crosslinking agent. This type of adverse effect is taught in patent application WO2016204951a1, which shows: (a) DSTDP can have an adverse effect on the degree of crosslinking retained after long term storage at elevated temperatures of 70 ℃ (as measured by maximum torque (MH) using a moving die rheometer); and (b) inclusion of Uvinul 4050 may improve retention of MH over time at elevated temperatures of 70 ℃.

In table 5 above, the comparative compound contains Uvinul 4050. Although compounds 1 to 4 according to the invention do not contain Uvinul 4050, they still exhibit the same or a higher degree of crosslinking after long-term storage at 70 ℃. The retained MH value reflects the amount of peroxide present in the formulation at the time of testing, with higher values of MH corresponding to more peroxide present. Each of compounds 1-4 of the present invention exhibited a 100% retention of MH, indicating that all or substantially all of the peroxide remained present in the composition of the present invention.

It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.