Polyaminosiloxane water tree inhibitor for electrical insulation

Abstract

A crosslinkable composition comprising an ethylene-based polymer, an aminosilane, and optionally a peroxide. The aminosilane has the formula (I): [Formula 1] JPEG2024500212000025.jpg16170 wherein R1, R2, and R3 are the same or different and each independently represents hydrogen and C1-C 20 alkyl groups, Y1 is selected from the group consisting of alkyl groups and alkoxy groups, Y2 is selected from the group consisting of alkyl groups and aminoalkyl groups, and n is 0 or 1. Also disclosed is a crosslinked composition formed from the crosslinkable composition.

Description

[Background technology]

[0001] Cross-linked ethylene polymers (XLPE) are known for use in wire and cable insulation. As an insulator, XLPE offers a variety of physical and electrical properties, such as resistance to mechanical cut, stress cracking and dielectric breakdown.

[0002] XLPE insulation in medium voltage (MV, 5-69 kV) and high voltage (HV, 70-225 kV) and extra high voltage (EHV, >225 kV) cables is particularly susceptible to the phenomenon of treeing. The term "treeing" is the deterioration of electrical insulating material with the appearance of dendritic paths through the insulating material, XLPE. Treeing is problematic because it is an electrical breakdown of the XLPE insulation. "Water trees" arise from water, voids, contaminants and / or defects present in the insulating material under an AC electric field. Water trees grow in the direction of the electric field and arise from imperfections which have the effect of increasing electrical stress at localized sites. The branches of water trees are narrow, on the order of 0.05 microns. Water trees increase in length with increasing time, frequency and voltage. Water trees are harmful because they are conductive and can reduce the insulating performance of the insulation layer and ultimately cause the failure of the cable.

[0003] "Electrical trees" are the result of internal electrical discharges that degrade insulating materials. Electrical trees result from localized heating, thermal decomposition, mechanical damage due to electrical stress, small voids, and / or the entrapment of contaminants in the surrounding air.

[0004] The art has recognized a need for treeing resistant wire and cable insulation materials. Further, a need has been recognized for treeing resistant XPLE insulation materials that have low dissipation factor while maintaining mechanical strength, crack resistance, and adequate cross-linking capability to maintain dielectric breakdown. Summary of the Invention

[0005] The present disclosure provides a composition. In one embodiment, the composition is a crosslinkable composition and includes an ethylene-based polymer, an aminosilane, and optionally a peroxide. The aminosilane is represented by the formula (I): [ka] (In the formula, R 1 , R 2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 20 alkyl groups, Y 1 is selected from the group consisting of alkyl groups and alkoxy groups; Y 2 is selected from the group consisting of alkyl groups and aminoalkyl groups; n is 0 or 1).

[0006] The present disclosure provides another aqueous composition. In one embodiment, a crosslinked composition is provided, comprising an ethylene-based polymer and an aminosilane. The aminosilane is represented by the formula (I): [ka] (In the formula, R 1 , R 2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 20 alkyl groups, Y 1 is selected from the group consisting of alkyl groups and alkoxy groups; Y 2 is selected from the group consisting of alkyl groups and aminoalkyl groups; n is 0 or 1).

[0007] definition Any reference to the Periodic Table of the Elements is to that published by CRC Press, Inc., 1990-1991. References to element groups in this table are by the new notation for numbering groups.

[0008] 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 U.S. version thereof is so incorporated by reference), particularly with respect to disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure).

[0009] Numerical ranges disclosed herein include all values ​​between and including the lower and upper limits, and in the case of ranges including explicit values ​​(e.g., 1 or 2, or 3-5, or 6, or 7), all subranges between any two explicit values ​​are included (e.g., the range 1-7 above includes subranges 1-2, 2-6, 5-7, 3-7, 5-6, etc.).

[0010] Unless specifically stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are by weight and all testing methods are current as of the filing date of this disclosure.

[0011] An "alkyl group" is a saturated linear, cyclic or branched hydrocarbon group. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), and the like.

[0012] An "aminoalkyl group" is an alkyl group that contains one or more amino groups.

[0013] An "amino group" is a nitrogen atom attached by a single bond to a hydrogen atom and / or a hydrocarbon.

[0014] An "aminosilane" is a silane that contains one or more primary and / or secondary amino groups.

[0015] As used herein, the term "blend" or "polymer blend" refers to a mixture of two or more polymers. A blend may or may not be miscible (not phase separated at the molecular level). A blend may or may not be phase separated. A blend may or may not contain one or more domain configurations as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and other methods known in the art. A blend may be made by physically mixing two or more polymers at a macro level (e.g., melt blending or compounding of resins) or at a micro level (e.g., co-forming in the same reactor).

[0016] The term "composition" refers to a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0017] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether specifically disclosed or not. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless specifically stated to the contrary. In contrast, the term "consisting essentially of" excludes any other component, step, or procedure from the scope of any succeeding description, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not expressly delineated or listed. The term "or" refers to the listed members individually as well as in any combination, unless otherwise stated. The use of the singular includes the use of the plural, and vice versa.

[0018] An "ethylene-based polymer" is a polymer that contains greater than 50 weight percent (wt%) polymerized ethylene monomer (based on the total amount of polymerizable monomers) and, optionally, may contain at least one comonomer. Ethylene-based polymers include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene-based polymer" and "polyethylene" may be used interchangeably.

[0019] As used herein, the term “ethylene monomer” or “ethylene” refers to a chemical unit having two carbon atoms with a double bond between them, and each carbon bonded to two hydrogen atoms, that can be polymerized with other such chemical units to form an ethylene-based polymer composition.

[0020] A "heteroatom" is an atom other than carbon or hydrogen. Heteroatoms can be non-carbon atoms from Groups IV, V, VI, and VII of the periodic table. Non-limiting examples of heteroatoms include F, N, O, P, B, S, and Si.

[0021] A "hydrocarbon" is a compound containing only hydrogen and carbon atoms. A "hydrocarbonyl" (or "hydrocarbonyl group") is a hydrocarbon having a valency (typically monovalent). The hydrocarbon can have a linear, cyclic, or branched structure.

[0022] As used herein, the term "linear low density polyethylene" (LLDPE) refers to a polyethylene having units derived from ethylene and at least one C 3 ~C 10 Alpha olefin or C 4 ~C 8LLDPE refers to linear ethylene / α-olefin copolymers containing a heterogeneous distribution of short chain branches, including units derived from an α-olefin comonomer. LLDPE is characterized by the presence of little, if any, long chain branching, in contrast to conventional LDPE. LLDPE has a density of less than 0.910 g / cc to 0.940 g / cc. Non-limiting examples of LLDPE include TUFLIN™ Linear Low Density Polyethylene Resins (available from The Dow Chemical Company), DOWLEX™ Polyethylene Resins (available from the Dow Chemical Company), and MARLEX™ Polyethylene (available from Chevron Phillips).

[0023] As used herein, the term "low density polyethylene" (or LDPE) refers to polyethylene having a density of 0.910 g / cc to less than 0.940 g / cc, or 0.918 g / cc to 0.930 g / cc, and long chain branching with a broad molecular weight distribution (MWD), i.e., a "broad MWD" of 4.0 to 20.0.

[0024] An "olefin" is an unsaturated aliphatic hydrocarbon containing a carbon-carbon double bond.

[0025] The term "phenyl" (or "phenyl group") refers to a C 6 H 5 It is an aromatic hydrocarbon ring.

[0026] As used herein, the term "polymer" or "polymeric material" refers to a compound prepared by polymerizing monomers, whether of the same or different types, to provide in polymerized form the multiple and / or repeating "units" or "mer units" that make up the polymer. Thus, the term polymer in general encompasses the term homopolymer, which is commonly used to refer to a polymer prepared from only one type of monomer, and the term copolymer, which is commonly used to refer to a polymer prepared from at least two types of monomer. It also encompasses all forms of copolymers, e.g., random, block, etc. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" refer to the above-mentioned copolymers prepared from polymerizing ethylene or propylene, respectively, with one or more additional polymerizable α-olefin monomers. It should be noted that although polymers are often referred to as "made of" one or more particular monomers, "based on" a particular monomer or monomer type, "containing" a particular monomer content, etc., in this context, the term "monomer" is understood to refer to the polymerized residue of a particular monomer and not to the unpolymerized species. Generally, polymers are referred to herein in terms of "units" that are the polymerized form of the corresponding monomers.

[0027] As used herein, a "silane" is a compound having one or more Si-C bonds.

[0028] Test Method Density is measured according to ASTM D792, Method B. Results are reported in grams per cubic centimeter (g / cc).

[0029] The dielectric constant and dissipation factor tests were performed at 50Hz on a high-precision high-voltage capacitance bridge QS87 from Shanghai Young Electrical Co. Ltd. with electrodes containing the specimen holder in an oven according to ASTM D150-11, Standard Test Method for AC Loss Characterization and Permittivity (Dielectric Constant) of Solid Electrical Insulation, and the high-voltage power was YG8Q from Shanghai Young Electrical Co. Ltd. The specimens are cured (crosslinked) compression molded plaques prepared by crosslinked polyolefin products and compression molded plaque preparation method 1. The plaques are degassed under atmospheric pressure in a vacuum oven at 70°C for 24 hours. The specimens are trimmed, tested for thickness, and sandwiched between two electrodes in a 110°C oven immediately after the electrode temperature reaches 100°C. Potentials were set across the film at 2.5 kilovolts (kV), 5 kV, 7.5 kV, 11 kV, 7.5 kV, 5 kV, and 2.5 kV (all at 50 Hertz), and the electrical stress on the film was calculated as equal to the voltage applied across the film divided by the thickness of the film in millimeters (mm), and the dielectric loss tangent ("DF") and dielectric constant (i.e., dielectric constant, ε r ) is tested. Dielectric loss tangent (DF) curves at different electrical stress values, typically plotted over the range of 5 kV / mm to 30 kV / mm, are obtained. From the curves, the DF value when the electrical stress is equal to 25 kV / mm is calculated.

[0030] Melt Index

[0031] As used herein, the term "melt index" or "MI" refers to a measure of how easily a thermoplastic polymer flows when in a molten state. Melt index, or MI, is a measure of how easily a thermoplastic polymer flows when in a molten state. 2 is determined according to ASTM D 1238, condition 190°C / 2.16 kg and reported in grams dissolving per 10 minutes (g / 10 min). I10 is determined according to ASTM D 1238, condition 190°C / 10 kg and reported in grams dissolving per 10 minutes (g / 10 min).

[0032] Moving Die Rheometer (MDR) Testing

[0033] MDR testing was performed on an MDR2000 (Alpha Technologies) at 180°C for 20 minutes while monitoring the change in torque according to ASTM D5289-12, Standard Test Method for Rubber Property-Vulcanization Using Rotorless Cure Meters. The minimum measured torque value is indicated as "ML" expressed in deciNewton-meter (dN-m). As the curing or crosslinking progresses, the measured torque value increases and eventually reaches a maximum torque value. The maximum or highest measured torque value is indicated as "MH" expressed in dN-m. All other conditions being equal, the higher the MH torque value, the higher the degree of crosslinking. The T90 crosslinking time is determined as the number of minutes required to achieve a torque value equal to 90% of the difference between MH minus ML (MH-ML), i.e., 90% of the way from ML to MH. The shorter the T90 crosslinking time, i.e., the faster the torque value is 90% of the way from ML to MH, the faster the cure rate of the test specimen. Conversely, the longer the T90 crosslinking time, ie, the longer it takes for the torque value to gain 90% of the way from ML to MH, the slower the cure rate of the test specimen.

[0034] The water tree growth test method was measured according to ASTM D6097-01a, Standard Test Method for Relative Resistance to Vented Water-Tree Growth in Solid Dielectric Insulating Materials. This test method targets the relative resistance to water tree growth of translucent thermoplastic or crosslinked electrical insulating materials. It is particularly applicable to extruded polymeric insulating materials useful for medium voltage power cables. Ten compression molded disk specimens each containing a controlled cone-shaped defect are subjected to an applied voltage of 5 kilovolts (kV) at 1 kilohertz (kHz) and 23°±2° in a conductive aqueous solution of 0.01 normal sodium chloride for 30 days. The controlled cone-shaped defect is formed by a sharp needle with a 60° included angle and a 3 micrometer (μm) tip radius. This results in an enhanced electrical stress at the defect tip, which is estimated by Mason's hyperbolic point-to-face stress enhancement equation. This enhanced electrical stress initiates the formation of a vented water tree growing from the defect tip. Each of the resulting tree specimens so produced is stained and sliced. The water tree length and point-to-face thickness of the specimen are measured under a microscope and used to calculate a ratio defined as the resistance to water tree growth. Water tree length (WTL) is the percentage of the thickness of the insulating material through which the water trees have grown. The lower the WTL value, the better the water tree resistance. WTL is reported as a percentage (%). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0035] 1. Crosslinkable composition The present disclosure provides a composition. In one embodiment, the composition is a crosslinkable composition and includes an ethylene-based polymer, an aminosilane, and optionally a peroxide. The aminosilane is represented by the formula (I): [ka] (In the formula, R 1 , R 2 , and R3 are the same or different and each independently represent hydrogen and C 1 -C 20 alkyl groups, Y 1 is selected from the group consisting of alkyl groups and alkoxy groups; Y 2 is selected from the group consisting of alkyl groups and aminoalkyl groups; n is 0 or 1).

[0036] The present disclosure provides a composition that is a crosslinkable composition. A "crosslinkable composition," as used herein, is a composition that contains an ethylene-based polymer and one or more additives (e.g., free radical initiators or organic peroxides) that enhance the ability of the ethylene-based polymer to crosslink when subjected to crosslinking conditions (e.g., heat, irradiation, and / or UV light). After being subjected to crosslinking conditions (e.g., "post-crosslinking" or "post-curing"), the crosslinkable composition becomes a "crosslinked composition" that includes an ethylene-based polymer that is crosslinked and structurally and physically distinct from the crosslinkable composition.

[0037] The crosslinkable composition comprises an ethylene-based polymer. Non-limiting examples of suitable ethylene-based polymers include ethylene homopolymer, ethylene / α-olefin copolymer (linear or branched), high density polyethylene ("HDPE"), low density polyethylene ("LDPE"), linear low density polyethylene ("LLDPE"), medium density polyethylene ("MDPE"), and combinations thereof. The crosslinkable composition contains 50% to 99% by weight, or 80% to 99% by weight, or 90% to 99% by weight, or 95% to 99% by weight of the ethylene-based polymer, based on the total weight of the crosslinkable composition.

[0038] In one embodiment, the ethylene-based polymer is ethylene / C 3 -C 20 Ethylene / C copolymers having an α-olefin content of 1 wt.% to 45 wt.%, or 5 wt.% to 40 wt.%, or 10 wt.% to 35 wt.%, or 15 wt.% to 30 wt.%, based on the total weight of the α-olefin copolymer.3 -C 20 α-Olefin Copolymer, or Ethylene / C 4 -C 8 It is an α-olefin copolymer. 3 -C 20 Non-limiting examples of α-olefins include propene, butene, 4-methyl-1-pentene, hexene, octene, decene, dodecene, tetradecene, hexadecene, and octadecene. The α-olefins may also have cyclic structures, such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinylcyclohexane. Suitable ethylene / C 3 -C 20 Non-limiting examples of α-olefin copolymers include ethylene / propylene copolymers, ethylene / butene copolymers, ethylene / hexene copolymers, and ethylene / octene copolymers.

[0039] In one embodiment, the ethylene-based polymer comprises a non-conjugated diene comonomer. Suitable non-conjugated dienes include linear, branched, or cyclic hydrocarbon dienes having 6 to 15 carbon atoms. Examples of suitable non-conjugated dienes include linear acyclic dienes such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, and 1,9-decadiene; branched acyclic dienes such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, and mixed isomers of dihydromyricene and dihydroocinene; monocyclic alicyclic dienes such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,5-cyclododecadiene; and polycyclic alicyclic fused and bridged isomers. Ring dienes, such as, but not limited to, tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, and bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl, and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene.

[0040] In one embodiment, the ethylene-based polymer is an ethylene / propylene / diene terpolymer (or "EPDM"). Non-limiting examples of suitable dienes include 1,4-hexadiene ("HD"), 5-ethylidene-2-norbornene ("ENB"), 5-vinylidene-2-norbornene ("VNB"), 5-methylene-2-norbornene ("MNB"), and dicyclopentadiene ("DCPD"). The diene content of the EPDM is from 0.1% to 10.0% by weight, or from 0.2% to 5.0% by weight, or from 0.3% to 3.0% by weight, based on the total weight of the EPDM.

[0041] In one embodiment, the ethylene-based polymer comprises units derived from ethylene and units derived from at least one comonomer having structure (A): [ka] and In the formula, R 1 is C 1 -C 4 is a hydrocarbyl group, R 2 is C 1 -C 2 It is a hydrocarbyl group.

[0042] Suitable R 1 Non-limiting examples of groups include unsubstituted C aryl groups, including methyl, ethyl, propyl, butyl, ethenyl, propenyl, and butenyl groups. 1 -C 4 Alkyl groups and unsubstituted C 2 -C 4 Alkenyl groups include unsubstituted C 1 -C 4 Alkyl groups and unsubstituted C 2 -C 4 The alkenyl group can be branched or linear. In one embodiment, R 1 The group may be, for example, a methyl group, an ethyl group, a propyl group, a butyl group, or an ethenyl group. 1 -C 4 In a further embodiment, R 1 The groups are selected from methyl, ethyl, butyl, and ethenyl groups. 1 The groups are selected from methyl groups, ethyl groups, and straight-chain butyl groups.

[0043] Suitable R 2 Non-limiting examples of unsubstituted C include methyl, ethyl, and ethenyl groups. 1 -C 2 Alkyl groups and unsubstituted C 2 In one embodiment, R 2The groups are selected from methyl groups and unsubstituted ethene groups.

[0044] In one embodiment, the ethylene-based polymer comprises: (i) one or more hydrolyzable silyl groups, each of which is independently represented by the formula (R 2 ) m (R 3 ) 3-m where subscript m is an integer of 1, 2, or 3; and each R 2 are independently H, HO-, (C 1 -C 6 ) alkoxy, (C 2 -C 6 )Carboxy, phenoxy, (C 1 -C 6 ) alkyl-phenoxy, ((C 1 -C 6 ) alkyl) N-, (C 1 -C 6 ) alkyl(H)C=NO-, or ((C 1 -C 6 )Alkyl) 2 C=NO-, and each R 3 are independently 1 -C 6 ) one or more hydrolyzable silyl groups, which are alkyl or phenyl; (ii) C 3 -C 40 α-olefin comonomers; (iii) Both (i) and (ii). Each R 2 may be free of H and HO-, or free of phenoxy and (C1-C9) alkyl-phenoxy. 2 are independently 1 -C 6 ) alkoxy, (C 2 -C 6 ) carboxy, ((C 1 -C 6 )Alkyl) 2 N-, (C 1 -C 9 ) alkyl(H)C=NO-, or ((C 1 -C 9)Alkyl) 2 C=NO-; or (C 1 -C 9 )alkoxy; or (C 2 -C 9 ) carboxy; or ((C 1 -C 9 )Alkyl) 2 N-; or (C 1 -C 9 ) alkyl(H)C=NO-; or ((C 1 -C 9 )Alkyl) 2 C=NO- is also acceptable.

[0045] In one embodiment, the ethylene-based polymer is a low density polyethylene (LDPE) homopolymer having one, some, or all of the following characteristics: (i) a density of 0.91 to 0.93; and / or (ii) A melt index of 0.5 g / 10 min to 10.0 g / 10 min, or 1.0 g / 10 min to 5.0 g / 10 min.

[0046] The crosslinkable composition comprises an aminosilane. The aminosilane has the formula (I): [ka] (In the formula, R 1 , R 2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 20 alkyl groups, Y 1 is selected from the group consisting of alkyl groups and alkoxy groups; Y 2 is selected from the group consisting of alkyl groups and aminoalkyl groups; (n is 0 or 1). The crosslinkable composition comprises 0.1 wt % to 1.0 wt %, or 0.1 wt % to 0.9 wt %, or 0.2 wt % to 0.8 wt %, or 0.3 wt % to 0.7 wt % of the aminosilane. The weight percentages are based on the total weight of the crosslinkable composition.

[0047] R 1 , R 2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 20 In one embodiment, R 1 , R 2 , and R 3 are identical, and each is C 1 -C 4 In a further embodiment, R is selected from alkyl groups, such as methyl, ethyl, propyl, and butyl groups. 1 , R 2 , and R 3 are identical and each is a methyl group.

[0048] In one embodiment, the crosslinkable composition has formula (I): [ka] (In the formula, R 1 , R 2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 4 alkyl groups, Y 1 is C 1 -C 4 is an alkyl group, Y 2 is selected from the group consisting of alkyl groups and aminoalkyl groups; n is 1).

[0049] In one embodiment, the crosslinkable composition has formula (I): [ka] (In the formula, R 1 , R 2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 4 alkyl groups, Y 1 is C 1 -C 4 is an alkoxy group, Y 2 is selected from the group consisting of alkyl groups and aminoalkyl groups; n is 1).

[0050] In one embodiment, the crosslinkable composition has formula (I): [ka] (In the formula, R 1 , R 2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 4 alkyl groups, and n is 0.

[0051] Non-limiting examples of suitable aminosilanes of formula (I) include 3-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, 3-(m-aminophenoxy)propyltrimethoxysilane, and combinations thereof.

[0052] In one embodiment, the aminosilane of formula (I) is 3-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, and combinations thereof.

[0053] In one embodiment, the aminosilane of formula (I) is p-aminophenyltrimethoxysilane.

[0054] In addition to the ethylene-based polymer and the aminosilane of formula (I), the crosslinkable composition optionally includes a free radical initiator. In one embodiment, a free radical initiator is present in the crosslinkable composition, and the free radical initiator is an organic peroxide. An organic peroxide is a molecule, or a collection of such molecules, that contains carbon atoms, hydrogen atoms, and two or more oxygen atoms and has at least one -OO- group, where if more than one -OO- group is present, each -OO- group is indirectly bonded to another -OO- group through one or more carbon atoms. Non-limiting examples of suitable organic peroxides include diacyl peroxides, peroxycarbonates, peroxydicarbonates, peroxyesters, peroxyketals, cyclic ketone peroxides, dialkyl peroxides, ketone peroxides, and combinations thereof. When an organic peroxide is present, the crosslinkable composition includes from greater than 0% to less than 2% by weight, or from 0.1% to 1.9% by weight, or from 0.2 to 1.8% by weight, based on the total weight of the crosslinkable composition. It is understood that the aggregate of the ethylene-based polymer, the aminosilane of formula (I), and the peroxide makes up 100% by weight of the crosslinkable composition.

[0055] The organic peroxides are represented by the formula R O -OOR O where each R O are independently 1 -C 20 ) alkyl group or (C 6 -C 20 ) an aryl group. 1 -C 20 ) alkyl groups are independently unsubstituted or have one or two (C 6 -C 12 ) substituted with an aryl group. 6 -C 20 The aryl group is unsubstituted or contains 1 to 4 (C 1 -C 10) alkyl group. Alternatively, the organic peroxide may be of the formula R O -OOROOR O wherein R is a diperoxide of 2 -C 10 ) alkylene, (C 3 -C 10 ) a divalent hydrocarbon group such as cycloalkylene or phenylene, and each R O is as defined above.

[0056] Non-limiting examples of suitable organic peroxides include dicumyl peroxide (DCP), lauryl peroxide, benzoyl peroxide, tert-butyl perbenzoate, di(tert-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, tert-butyl hydroperoxide, isopropyl percarbonate, α,α'-bis(tert-butylperoxide), α,α'-bis(t-butylperoxy)-p-diisopropylbenzene, bis(1,1-dimethylethyl)peroxide, bis(1,1-dimethylpropyl)peroxide, 2,5-dimethyl-2,5-bis(1,1-dimethyl 2,5-Dimethyl-2,5-bis(1,1-dimethylethylperoxy)hexane, 2,5-Dimethyl-2,5-bis(1,1-dimethylethylperoxy)hexyne, 4,4-Bis(1,1-dimethylethylperoxy)valeric acid, butyl ester, 1,1-Bis(1,1-dimethylethylperoxy)-3,3,5-trimethylcyclohexane, Benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-amyl peroxide ("DTAP"), bis(alpha-t-butyl-peroxyisopropyl)benzene ("BIPB") , isopropyl cumyl t-butyl peroxide, t-butyl cumyl peroxide, di-t-butyl peroxide, 2,5-bis(t-butylperoxy)-2,5-dimethylhexane, 2,5-bis(t-butylperoxy)-2,5-dimethylhexyne-3,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, isopropyl cumyl t-butyl peroxide, 4,4-di(tert-butylperoxy)butyl valerate, di(isopropyl cumyl)peroxide, and the like.

[0057] In one embodiment, a free radical initiator is present in the crosslinkable composition, and the free radical initiator is an organic peroxide that is dicumyl peroxide (DCP).

[0058] The crosslinkable composition may include one or more optional additives. When additives are present, non-limiting examples of suitable additives include antioxidants, scorch retarders, crosslinking coagents (e.g., triallyl isocyanurate, triallyl trimellitate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethylacrylate, ethoxylated bisphenol A dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, N,N,N',N',N'',N''-hexaaryl-1, 3,5-triazine-2,4,6-triamine, tris(2-hydroxyethyl)isocyanurate triacrylate, propoxylated glyceryl triacrylate, 2,4-diphenyl-4-methyl-1-pentene, 1,3-diisopropenylbenzene, tetramethyltetravinylcyclotetrasiloxane, trivinyltrimethylcyclotrisiloxane, pentavinylpentamethylcyclopentasiloxane), nucleating agents, processing aids, extender oils, carbon black, nanoparticles, UV stabilizers, and combinations thereof.

[0059] In one embodiment, the crosslinkable composition includes one or more antioxidants. Non-limiting examples of suitable antioxidants include bis(4-(1-methyl-1-phenylethyl)phenyl)amine (e.g., NAUGARD 445), 2,2-methylene-bis(4-methyl-6-t-butylphenol) (e.g., VANOX MBPC), 2,2'-thiobis(2-t-butyl-5-methylphenol (CAS No. 90-66-4, CAS No. 96-69-5, commercially available from LOWINOX TBM-6), 2,2'-thiobis(6-t-butyl-4-methylphenol (CAS No. 90-66-4, commercially available from LOWINOX TBM-6), and 2,2'-thiobis(6-t-butyl-4-methylphenol) (CAS No. 90-66-4, commercially available from LOWINOX TBM-6). TBP-6), tris[(4-tert-butyl-3-hydroxy-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 number 6683-19-8), 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid 2,2'-thiodiethanediyl ester (e.g., IRGANOX 1035, CAS number 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), 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, Cyanox 1790 (CAS: 40601-76-1), Uvinul 4050 (CAS: 124172-53-8), and combinations thereof. The antioxidant is present in an amount of 0.01% to 1.5% by weight, or 0.05% to 1.2% by weight, or 0.07% to 1.0% by weight, or 0.1% to 0.5% by weight, based on the total weight of the crosslinkable composition.

[0060] In one embodiment, the crosslinkable composition comprises 80% to 99% by weight, or 90% to 99% by weight, or 95% to 99% by weight of an ethylene-based polymer; 0.1% to 1.0% by weight, or 0.1% to 0.9% by weight, or 0.2% to 0.8% by weight, or 0.3% to 0.7% by weight of an aminosilane, and More than 0 wt.% and less than 2 wt.%, or 0.5 wt.% to 1.9 wt.% peroxide, the weight percentages being based on the total weight of the crosslinkable composition, it being understood that the aggregate of the ethylene-based polymer, aminosilane, and peroxide amounts to 100 wt.% of the crosslinkable composition.

[0061] The components of the crosslinkable composition are processed and mixed to cure the crosslinkable composition and form a crosslinked composition. Pellets of the ethylene-based polymer are fed into a mixing device (e.g., a Brabender mixer, etc.) at a temperature of 120°C to 180°C to melt the ethylene-based polymer. The aminosilane (and optional additives such as antioxidants) are fed into the mixing device and melt mixed into the ethylene-based polymer. The mixed compound (hereinafter "AS-PE compound") consisting of the ethylene-based polymer and the aminosilane (and optional additives) is recovered and cut into small pieces.

[0062] The mixing of the AS-PE compound with the free radical initiator is carried out by placing small pieces of the AS-PE compound and peroxide (and optionally an antioxidant) in a container. The container is then shaken, rotated, tumbled, or otherwise agitated so that the peroxide is held in contact with the AS-PE compound pieces or is otherwise absorbed by the AS-PE compound pieces. The process involves heating the mixture of the AS-PE compound and peroxide at a temperature of 60°C, or 70°C, or 80°C to 90°C, or 100°C, or otherwise above the melting temperature of the peroxide. Heating the mixture is carried out for a period of 1 minute, or 10 minutes, or 30 minutes to 1 hour, or 2 hours, or 3 hours, or 4 hours, or 5 hours, or 6 hours, or 7 hours, or 8 hours, thereby allowing the peroxide to diffuse into the AS-PE compound pellets.

[0063] In one embodiment, the mixing and heating are performed sequentially.

[0064] In one embodiment, the mixing and heating are performed simultaneously.

[0065] The peroxide-containing AS-PE pieces are cured (i.e., "crosslinked") by heating at a cure temperature of 100°C, or 110°C, or 125°C to 150°C, or 180°C, or 200°C for 1 minute, or 5 minutes, or 10 minutes, or 30 minutes, or 1 hour to 2 hours, or 5 hours, or 7 hours, or more, to form a crosslinked composition consisting of the ethylene-based polymer, the aminosilane, and optional additives. The crosslinked composition is structurally and physically distinct from the crosslinkable composition.

[0066] 2. Crosslinked composition In one embodiment, a crosslinking composition is provided. The crosslinking composition includes an ethylene-based polymer, an aminosilane, and an optional additive. The aminosilane is represented by the formula (I): [ka] (In the formula, R 1 , R2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 20 alkyl groups, Y 1 is selected from the group consisting of alkyl groups and alkoxy groups; Y 2 is selected from the group consisting of alkyl groups and aminoalkyl groups; n is 0 or 1).

[0067] The ethylene-based polymer in the crosslinked composition can be any ethylene-based polymer in the crosslinkable composition disclosed hereinabove. In one embodiment, the ethylene-based polymer of the crosslinked composition is a LDPE ethylene homopolymer having a density of 0.91 g / cc to 0.93 g / cc and a melt index of 0.5 g / 10 min to 5.0 g / 10 min.

[0068] In one embodiment, the crosslinking composition comprises: 90% to 99.9% by weight, or 90% to 99% by weight, or 95% to 99% by weight of an ethylene-based polymer; 0.1% to 1.0% by weight, or 0.1% to 0.9% by weight, or 0.2% to 0.8% by weight, or 0.3% to 0.7% by weight of the aminosilane of formula (I), where the weight percentages are based on the total weight of the crosslinking composition. [ka] (In the formula, R 1 , R 2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 20 alkyl groups, Y 1 is selected from the group consisting of alkyl groups and alkoxy groups; Y 2 is selected from the group consisting of alkyl groups and aminoalkyl groups; n is 0 or 1, The crosslinking composition comprises (i) an average WTL of less than 10%, or between 1% and 8%, and (ii) Dissipation factor (DF) of less than 0.1% or 0.01% to 0.09% It is understood that the aggregate of the ethylene-based polymer, the aminosilane of formula (I), and the optional additives makes up 100% by weight of the crosslinked composition.

[0069] In one embodiment, the crosslinking composition comprises: 90% to 99.9% by weight, or 90% to 99% by weight, or 95% to 99% by weight of an ethylene-based polymer; 0.1% to 1.0% by weight, or 0.1% to 0.9% by weight, or 0.2% to 0.8% by weight, or 0.3% to 0.7% by weight of the aminosilane of formula (I), where the weight percentages are based on the total weight of the crosslinking composition. [ka] (In the formula, R 1 , R 2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 4 alkyl groups, Y 1 is C 1 -C 4 is an alkyl group, Y 2 is selected from the group consisting of alkyl groups and aminoalkyl groups; n is 1 The crosslinking composition comprises (i) an average WTL of less than 10%, or between 1% and 8%, and (ii) Dissipation factor (DF) of less than 0.1% or 0.01% to 0.09% It is understood that the aggregate of the ethylene-based polymer, the aminosilane of formula (I), and the optional additives makes up 100% by weight of the crosslinked composition.

[0070] In one embodiment, the crosslinking composition comprises: 90% to 99.9% by weight, or 90% to 99% by weight, or 95% to 99% by weight of an ethylene-based polymer; 0.1% to 1.0% by weight, or 0.1% to 0.9% by weight, or 0.2% to 0.8% by weight, or 0.3% to 0.7% by weight of the aminosilane of formula (I), where the weight percentages are based on the total weight of the crosslinking composition. [ka] (In the formula, R 1 , R 2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 4 alkyl groups, Y 1 is C 1 -C 4 is an alkoxy group, Y 2 is selected from the group consisting of alkyl groups and aminoalkyl groups; n is 1 The crosslinking composition comprises (i) an average WTL of less than 10%, or between 1% and 8%, and (ii) Dissipation factor (DF) of less than 0.1% or 0.01% to 0.09% It is understood that the aggregate of the ethylene-based polymer, the aminosilane of formula (I), and the optional additives makes up 100% by weight of the crosslinked composition.

[0071] In one embodiment, the crosslinking composition comprises: 90% to 99.9% by weight, or 90% to 99% by weight, or 95% to 99% by weight of an ethylene-based polymer; 0.1% to 1.0% by weight, or 0.1% to 0.9% by weight, or 0.2% to 0.8% by weight, or 0.3% to 0.7% by weight of the aminosilane of formula (I), where the weight percentages are based on the total weight of the crosslinking composition. [ka] (In the formula, R 1 , R 2 , and R 3 are the same or different and each independently represent hydrogen and C 1 -C 4 alkyl groups, n is 0, The crosslinking composition comprises (i) an average WTL of less than 10%, or between 1% and 8%, and (ii) Dissipation factor (DF) of less than 0.1% or 0.01% to 0.09% In a further embodiment, the aminosilane is p-aminophenyltrimethoxysilane. It is understood that the aggregate of the ethylene-based polymer, the aminosilane of formula (I), and optional additives represents 100% by weight of the crosslinked composition.

[0072] The crosslinking composition may include one or more optional additives. When an additive is present in the crosslinking composition, the additive may be any additive as in the crosslinkable composition disclosed herein above.

[0073] Purpose

[0074] The crosslinked compositions can be used in a variety of applications including, but not limited to, wire and cable applications such as insulation layers for AC (alternating current) and DC (direct current) MV / HV / EHV cables, carbon black filled semiconducting layers for MV / HV / EHV cables, accessories for power distribution transmission lines, insulation layers, insulating encapsulation films for photovoltaic (PV) modules, etc.

[0075] By way of example and not by way of limitation, several embodiments of the present disclosure will now be detailed in the following examples. EXAMPLES

[0076] The materials used in the examples are described in Table 1 below. [Table 1]

[0077] 1.Formulation LDPE1 pellets were fed into a Brabender mixer at a set temperature of 160°C and rotor speed of 10 rpm. Antioxidant (TBM-6) and ingredients from Table 1 were fed into the polymer melt at set temperatures to form individual samples with different ingredients from Table 1. The final mix was run for 4 minutes at set temperature and rotor speed of 45 rpm. The compound was collected and cut into small pieces for use.

[0078] 2. Pelletization The compound samples were fed into the hopper of a Brabender single screw extruder. The compound samples were extruded into molten strands at 120° C. with a screw speed of 25 rpm. The molten strands were fed into a Brabender pelletizer to prepare pellets.

[0079] 3.Soaking A 250 mL fluorinated HDPE bottle was applied to seal 50 g pellets and 0.865 g DCP. The bottle was tightly sealed. The reaction was carried out at 70° C. for 8 hours. The bottle was shaken every 0, 2, 5, 10, 20, 30 minutes during the soaking process. The DCP soaked pellets (XLPE pellets) were stored in the fluorinated bottle for testing after the soaking process.

[0080] 4. Hot press hardening of XLPE plaque The mold size / plaque sample size was 180 x 190 x 0.5 mm. 15 g of XLPE pellets were weighed and sandwiched between two pieces of 2 mm PET film. The sample and PET film were placed in the mold. The mold was then sandwiched between the top and bottom plates of a hot press machine and held at 120°C for 10 minutes with a pressure of 0 MPa for the preheat period. The temperature was heated from 120°C to 180°C within 7 minutes at 10 MPa to cure. The mold was held at 120°C and 5 MPa for 0.5 minutes. The mold was held at 120°C and 10 MPa for 0.5 minutes. After venting 8 times, the mold was held at 180°C and 10 MPa for 13 minutes to cure. The mold was cooled from 180°C to 60°C within 10 minutes at 10 MPa. The XLPE plaque was removed from the mold. Table 2 below provides the composition and properties for each individual sample. [Table 2] CS = Comparative sample; IE = Inventive example

[0081] Table 2 shows that IE1-2 have a combination of (i) low water tree length (WTL) of less than 10% (5.0% and 7.2%) and (ii) low DF of less than 0.1% (0.07% and 0.09%). In contrast, the comparative samples cannot achieve a low WTL of less than 10% and a low DF of less than 0.1%. The ability of the present crosslinkable composition having the aminosilane of formula (I) to obtain a crosslinked composition with low WTL and low DF without adversely affecting the crosslinking is unexpected.

[0082] The present disclosure is not limited to the embodiments and examples contained herein, but is specifically intended to include portions of the embodiments and modified forms of those embodiments, including combinations of elements of different embodiments, within the scope of the following claims.

Claims

1. 1. A crosslinkable composition comprising: an ethylene-based polymer; Aminosilanes having the formula (I) [Formula 1] (In the formula, R １ , R ２ , and R ３ are the same or different, and each independently represents hydrogen and C １ -C ２０ alkyl groups, Y １ is selected from the group consisting of alkyl groups and alkoxy groups; Y ２ is selected from the group consisting of alkyl groups and aminoalkyl groups; n is 0 or 1; Optionally with peroxide A crosslinkable composition comprising:

2. the ethylene-based polymer has a density from 0.91 g / cc to 0.93 g / cc; and Melt index: 0.5g / 10min to 5.0g / 10min The crosslinkable composition of claim 1 having the formula:

3. Aminosilanes having the formula (I) [chemical 2] (In the formula, R １ , R ２ , and R ３ are the same or different, and each independently represents hydrogen and C １ -C ４ alkyl groups, Y １ is C １ -C ４ is an alkyl group, Y ２ is selected from the group consisting of alkyl groups and aminoalkyl groups; 3. The crosslinkable composition of claim 1, wherein n is 1.

4. Aminosilanes having the formula (I) [C3] (In the formula, R １ , R ２ , and R ３ are the same or different, and each independently represents hydrogen and C １ -C ４ alkyl groups, Y １ is C １ -C ４ is an alkoxy group, Y ２ is selected from the group consisting of alkyl groups and aminoalkyl groups; 3. The crosslinkable composition of claim 1, wherein n is 1.

5. Aminosilanes having the formula (I) [C4] (In the formula, R １ , R ２ , and R ３ are the same or different, and each independently represents hydrogen and C １ -C ４ alkyl groups, The crosslinkable composition of claim 1 or 2, comprising:

6. 80% to 99% by weight of the ethylene-based polymer; 0.1% to 0.9% by weight of said aminosilane; Peroxides greater than 0% by weight and less than 2% by weight The crosslinkable composition according to any one of claims 1 to 5, comprising:

7. 7. The crosslinkable composition of any one of claims 1 to 6, comprising an additive selected from the group consisting of antioxidants, scorch retarders, crosslinking coagents, nucleating agents, processing aids, extender oils, carbon black, nanoparticles, UV stabilizers, and combinations thereof.

8. 1. A crosslinking composition comprising: an ethylene-based polymer; Aminosilanes having the formula (I) [C5] (In the formula, R １ , R ２ , and R ３ are the same or different, and each independently represents hydrogen and C １ -C ２０ alkyl groups, Y １ is selected from the group consisting of alkyl groups and alkoxy groups; Y ２ is selected from the group consisting of alkyl groups and aminoalkyl groups; n is 0 or 1; A crosslinking composition comprising:

9. the ethylene-based polymer has a density from 0.91 g / cc to 0.93 g / cc; and Melt index: 0.5g / 10min to 5.0g / 10min The crosslinked composition of claim 8 having the formula:

10. Aminosilanes having the formula (I) [C6] (In the formula, R １ , R ２ , and R ３ are the same or different, and each independently represents hydrogen and C １ -C ４ alkyl groups, Y １ is C １ -C ４ is an alkyl group, Y ２ is selected from the group consisting of alkyl groups and aminoalkyl groups; 10. The crosslinked composition of claim 8 or 9, comprising:

11. Aminosilanes having the formula (I) [C7] (In the formula, R １ , R ２ , and R ３ are the same or different, and each independently represents hydrogen and C １ -C ４ alkyl groups, Y １ is C １ -C ４ is an alkoxy group, Y ２ is selected from the group consisting of alkyl groups and aminoalkyl groups; 10. The crosslinked composition of claim 8 or 9, comprising:

12. Aminosilanes having the formula (I) [C8] (In the formula, R １ , R ２ , and R ３ are the same or different, and each independently represents hydrogen and C １ -C ４ alkyl groups, The crosslinked composition of claim 8 or 9, comprising:

13. 13. The crosslinked composition of any one of claims 8 to 12, comprising an additive selected from the group consisting of antioxidants, scorch retarders, crosslinking coagents, nucleating agents, processing aids, extender oils, carbon black, nanoparticles, UV stabilizers, and combinations thereof.

14. 90% to 99% by weight of the ethylene-based polymer; 0.1% to 1.0% by weight of the aminosilane; Including, The crosslinking composition comprises: (i) a mean WTL of less than 10.0%, and (ii) a dielectric loss tangent of less than 0.1% The crosslinked composition according to any one of claims 8 to 13, having the formula: