Polyaminosiloxane Water Tree Repellent for Electrical Insulation

Abstract

The present disclosure provides a composition. In an embodiment, the composition is a crosslinkable composition and includes an ethylene-based polymer, a polyaminosiloxane (PAS), and optionally a peroxide. The polyaminosiloxane (PAS) has the formula (I): [Formula 1] JPEG2024500602000049.jpg8170 During the ceremony, R is a C6-C 20 is an aminoalkyl group, Si is a silicon atom, O is an oxygen atom, Z is a hydrogen atom or a C1-C 10 is a hydrocarbonyl group, q, m, and n each independently represent an integer of 2 to 1,000,000; 1 / 2 represents an endblock structure of formula (II), [Case 2] JPEG2024500602000050.jpg16170 2 / 2 represents a linear structure of formula (III), [C3] JPEG2024500602000051.jpg16170 3 / 2 represents the branched structure of formula (IV). [C4] JPEG2024500602000052.jpg23170 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 cuts, stress cracking, and dielectric breakdown.

[0002] XLPE insulation in medium-voltage (MV, 5-69 kV), high-voltage (HV, 70-225 kV), and extra-high-voltage (EHV, over 225 kV) cables is particularly susceptible to treeing. The term "treeing" refers to the deterioration of electrical insulation material, resulting in the appearance of tree-like pathways through the XLPE insulation. Treeing is problematic because it is an electrical breakdown of the XLPE insulation. "Water trees" arise from water, voids, contaminants, and / or defects present within the insulation material under an AC electric field. Water trees grow in the direction of the electric field and result from defects that increase electrical stress at localized locations. Water tree branches 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 electrically conductive and can reduce the insulating capacity of the insulation layer, ultimately causing cable failure.

[0003] Electrical trees are the result of internal electrical discharges that decompose insulating materials. Electrical trees result from localized heating, thermal decomposition, mechanical damage due to electrical stress, small voids, and / or the inclusion 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 a low dissipation factor while maintaining adequate cross-linking capability to maintain mechanical strength, crack resistance, and dielectric breakdown. Summary of the Invention

[0005] The present disclosure provides a composition. In an embodiment, the composition is a crosslinkable composition and includes an ethylene-based polymer, a polyaminosiloxane (PAS), and optionally a peroxide. The polyaminosiloxane (PAS) has the formula (I): [ka] (In the formula, R is a C6-C 20 is an aminoalkyl group, Si is a silicon atom, O is an oxygen atom, Z is a hydrogen atom or a C1-C 10 is a hydrocarbonyl group, q, m, and n each independently represent an integer of 2 to 1,000,000; 1 / 2 represents the end block structure of formula (II), [ka] 2 / 2 represents the linear structure of formula (III), [ka] 3 / 2 represents the branched structure of formula (IV). [ka]

[0006] The present disclosure provides another aqueous composition. In one embodiment, a crosslinked composition is provided, comprising an ethylene-based polymer and a polyaminosiloxane (PAS). The polyaminosiloxane (PAS) has the formula (I): [ka] (In the formula, R is a C6-C 20 is an aminoalkyl group, Si is a silicon atom, O is an oxygen atom, Z is a hydrogen atom or a C1-C 10 is a hydrocarbonyl group, q, m, and n each independently represent an integer of 2 to 1,000,000; 1 / 2 represents the end block structure of formula (II), [ka] 2 / 2 represents the linear structure of formula (III), [ka] 3 / 2 represents the branched structure of formula (IV). [ka]

[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 United States version thereof is so incorporated by reference), particularly with respect to the 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. Ranges including explicit values ​​(e.g., 1 or 2, or 3 to 5, or 6, or 7) include all subranges between any two explicit values ​​(e.g., the 1 to 7 range above includes subranges such as 1 to 2, 2 to 65, 73 to 75, 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 test 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 "amino group" is a nitrogen atom attached by a single bond to a hydrogen atom and / or a hydrocarbon.

[0013] An "aminosiloxane" is a siloxane containing one or more primary and / or secondary amino groups.

[0014] As used herein, the terms "blend" or "polymer blend" refer 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. Blending may be achieved by physically mixing two or more polymers at a macro level (e.g., melt blending or compounding of resins) or a micro level (e.g., co-forming in the same reactor).

[0015] 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.

[0016] 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," unless otherwise stated, refers to the listed members individually as well as in any combination. The use of the singular includes the use of the plural, and vice versa.

[0017] 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 may optionally 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.

[0018] As used herein, the terms “ethylene monomer” or “ethylene” refer 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.

[0019] 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.

[0020] 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.

[0021] As used herein, the term "linear low density polyethylene" (or "linear low density polyethylene (LLDPE)") refers to a polyethylene having units derived from ethylene and at least one C3-C6 10 LLDPE refers to linear ethylene / α-olefin copolymers containing a heterogeneous distribution of short chain branches, including units derived from α-olefins or C4-C8 α-olefin comonomers. LLDPE is characterized by the presence of little, if any, long chain branching, in contrast to conventional LDPE. LLDPE has a density of 0.910 g / cc to less than 0.940 g / cc. Non-limiting examples of LLDPE include TUFLIN™ linear low density polyethylene resin (available from The Dow Chemical Company), DOWLEX™ polyethylene resin (available from The Dow Chemical Company), and MARLEX™ polyethylene (available from Chevron Phillips).

[0022] 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.

[0023] An "olefin" is an unsaturated aliphatic hydrocarbon containing a carbon-carbon double bond.

[0024] The term "phenyl" (or "phenyl group") is a C6H5 aromatic hydrocarbon ring having a valency (typically monovalent).

[0025] 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 general term polymer 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 aforementioned copolymers prepared from polymerizing ethylene or propylene with one or more additional polymerizable α-olefin monomers, respectively. While polymers are often referred to as "made of" one or more particular monomers, "based on" particular monomers or monomer types, "containing" particular monomer content, etc., it should be noted that 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 herein are referred to in terms of "units" that are the polymerized form of the corresponding monomers.

[0026] As used herein, a "silane" is a compound having one or more Si-C bonds.

[0027] As used herein, a "siloxane" is a hydrocarbon having an Si-O-Si bond.

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

[0029] Fourier Transform Infrared Analysis (FTIR)

[0030] The amount of terminal and internal trans double bonds per 1000 carbon atoms ("1000C") was determined by Fourier transform infrared analysis ("FTIR"). The sample to be analyzed was placed on a diamond / ZnSe crystal and appropriate pressure was applied to obtain optimal contact. ATR-FTIR spectra were then collected from 4000 to 650 cm-1, with eight scans for each sample. The experimental settings are listed below: resolution: 4.0 cm-1, apodization: strong scan, speed: 0.20 cm / s, detector: MIR TGS.

[0031] Gel Permeation Chromatography (GPC)

[0032] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) and a 4-capillary viscometer (DV) coupled to a Precision Detectors (now Agilent Technologies) two-angle laser light scattering (LS) detector model 2040. For all absolute light scattering measurements, a 15° angle was used. The autosampler oven compartment was set to 160°C, and the column compartment was set to 150°C. The columns used were four Agilent "Mixed A" 30 cm, 20 micrometer linear mixed-bed columns. The chromatographic solvent used was 1,2,4 trichlorobenzene (CAS 120-82-1, HPLC grade, Fisher Scientific) containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters and the flow rate was 1.0 milliliters / minute.

[0033] Calibration of the GPC column set was performed using at least 20 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000, arranged in six "cocktail" mixtures with at least 10 molecular weight intervals between each standard. Standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights above 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights below 1,000,000. The polystyrene standards were dissolved at 80°C for 30 minutes with gentle agitation. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).

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[0034] A polynomial between third and fifth order was used to fit each polyethylene-equivalent calibration point. A was adjusted slightly (to approximately 0.375-0.440) to correct for column resolution and band-broadening effects so that the homopolymer polyethylene standard had a molecular weight of 120,000.

[0035] Total plate counts for the GPC column set were performed using Eicosane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle agitation). Plate counts (Equation 2) and symmetry (Equation 3) were measured with a 200 microliter injection according to the following equations:

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[0036] Samples were prepared in a semi-automated fashion using the PolymerChar "Instrument Control" software, with a target sample weight of 2 mg / mL, and solvent (containing 200 ppm BHT) added via the PolymerChar high-temperature autosampler to a pre-nitrogen-sparged septa-capped vial. Samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0037] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation was based on GPC results using the PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from a narrow standard calibration curve for point (i) of Equation 1, according to Equations 4-6, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph.

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[0038] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (Flow Rate (Apparent)) for each sample by RV-matching the respective decane peak in the sample (RV (FM Sample)) with that of the decane peak in the narrow standard calibration (RV (FM Calibrated)). Any change in the time of the decane marker peak is then assumed to be related to a linear shift in flow rate (Flow Rate (Effective)) throughout the run. To facilitate the highest accuracy in the RV measurement of the flow rate marker peaks, a least-squares fitting routine is used to fit the peaks of the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on the flow rate marker peaks, the effective flow rate (relative to the narrow standard calibration) is calculated as shown in Equation 7. Processing of the flow rate marker peaks was performed via PolymerChar GPCOne™ software. An acceptable flow correction is such that the effective flow rate should be within + / - 2% of the apparent flow rate.

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[0039] Triple Detector GPC (TDGPC)

[0040] The chromatographic system, analytical conditions, column set, column calibration and calculation and distribution of conventional molecular weight moments were carried out according to the methods described in Gel Permeation Chromatography (GPC).

[0041] For the determination of viscometer and light scattering detector offsets from the IR5 detector, a systematic approach for the determination of multiple detector offsets was performed in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)) using PolymerChar GPCOne™ software to optimize triple detector log (MW and IV) results from broad homopolymer polyethylene standards (Mw / Mn>3) against narrow standard column calibration results from a narrow standard calibration curve.

[0042] Absolute molecular weight data were obtained using PolymerChar GPCOne™ software in a manner consistent with that published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injected concentration used in determining the molecular weight was obtained from the mass detector area and mass detector constant derived from a suitable linear polyethylene homopolymer or one of the polyethylene standards of known weight average molecular weight. Calculated molecular weights (using GPCOne™) were obtained using the light scattering constant and refractive index concentration coefficient, dn / dc, of 0.104, derived from one or more of the polyethylene standards described below. Generally, the mass detector response (IR5) and light scattering constant (determined using GPCOne™) should be determined from a linear standard with a molecular weight greater than approximately 50,000 g / mol. Viscometer calibration (determined using GPCOne™) can be achieved using the method described by the manufacturer, or alternatively, by using published values ​​of a suitable linear standard, such as Standard Reference Material (SRM) 1475a (available from the National Institute of Standards and Technology (NIST)). A viscometer constant (obtained using GPCOne™) is calculated, relating the specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity. The chromatographic concentration is assumed to be low enough to preclude addressing second viral coefficient effects (concentration effects on molecular weight).

[0043] Absolute weight average molecular weight (MW (Abs)) is obtained (using GPCOne™) from the light scattering (LS) area integrated chromatogram (factored by the light scattering constant) divided by the mass recovered from the mass constant and the mass detector (IR5) area. The molecular weight and intrinsic viscosity responses are linearly extrapolated (using GPCOne™) at the chromatographic end where the signal to noise is low. Each of the other moments Mn (Abs) and Mz (Abs) is calculated according to equations 8-9 as follows:

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[0044] gpcBR branching index by triple detector GPC (3D-GPC)

[0045] The gpcBR branching index is determined by first calibrating the light scattering, viscosity, and concentration detectors as described above. Baselines are then subtracted from the light scattering, viscometer, and concentration chromatograms. Integration windows are then set to ensure integration of all of the low molecular weight retention volume ranges of the light scattering and viscometer chromatograms, which indicate the presence of detectable polymer from the infrared (IR5) chromatogram. Linear polyethylene standards are then used to establish the Mark-Houwink constants for polyethylene and polystyrene. After obtaining the constants, the two values ​​are used to construct a conventional calibration method using two linear references for polyethylene molecular weight and polyethylene intrinsic viscosity as a function of elution volume, as shown in equations (10) and (11).

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[0046] 3D-GPC also independently obtains the intrinsic viscosity of the sample using equation (8). The area calculations in equations (5) and (8) provide greater accuracy because the overall sample area is much less susceptible to detector noise at the baseline and integration limits and variations caused by the 3D-GPC settings. More importantly, the peak area calculations are not affected by detector volume offsets. Similarly, the intrinsic viscosity (IV) of the sample can be obtained with high accuracy by the area method shown in equation (12).

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[0047] To determine the gpcBR branching index, the light scattering elution area of ​​the sample polymer is used to determine the molecular weight of the sample. The elution area of ​​the viscosity detector for the sample polymer is used to determine the intrinsic viscosity (IV or [η]) of the sample.

[0048] First, the molecular weight and intrinsic viscosity for a linear polyethylene standard sample, such as SRM1475a or equivalent, are determined using conventional calibration ("conventional calibration, cc") for both molecular weight and intrinsic viscosity as a function of elution volume.

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[0049] All statistical values ​​with a "cc" subscript are determined using the respective dissolution volume, the corresponding conventional calibration as described above, and the concentration (Ci). Values ​​without a subscript are measurements based on the mass detector, LALLS, and viscometer area. PE The values ​​of α and Log K are iteratively adjusted until the linear reference sample has a gpcBR measurement of zero. For example, the final values ​​of α and Log K for determining the gpcBR in this particular case are 0.725 and -3.391, respectively, for polyethylene and 0.722 and -3.993, respectively, for polystyrene. These polyethylene coefficients were then entered into Equation 13.

[0050] Once the K and α values ​​have been determined using the procedure described above, the procedure is repeated using a branched sample that is analyzed using the final Mark-Houwink constants obtained from the linear reference when the best "cc" calibration value is applied.

[0051] The interpretation of gpcBR is straightforward. For linear polymers, the values ​​measured by LS and viscometers will be close to conventional calibration standards, so the gpcBR calculated from Equation (14) will be close to zero. For branched polymers, the measured polymer molecular weight will be higher than the calculated Mw,cc, and the calculated IVcc will be higher than the measured polymer IV, especially at high levels of long-chain branching, so the gpcBR will be higher than zero. In effect, the gpcBR value represents the fractional change in IV due to the molecular size contraction effect as a result of polymer branching. A gpcBR value of 0.5 or 2.0 represents a molecular size contraction effect on IV at a level of 50% and 200%, respectively, relative to an equivalent weight of linear polymer molecules.

[0052] The sample was dissolved in THF at a concentration of approximately 5 mg / mL. The sample solution was filtered through a 0.45 μm PTFE membrane prior to SEC analysis. Instrument: Agilent 1200; Column: Two mixed-E columns (7.8 × 300 mm); Column temperature: 35 °C; Mobile phase: Tetrahydrofuran; Flow rate: 1.0 mL / min; Injection volume: 50 μL; Detector: Agilent refractive index detector, 35 °C; Software: Agilent GPC software; Calibration curve: PL polystyrene narrow standards (part number 2010-0101) with polyol equivalent molecular weights ranging from 11,450 to 162 g / mol.

[0053] Melt Index

[0054] 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 I2, is measured in accordance with ASTM D 1238, Condition 190°C / 2.16 kg, and is reported in grams dissolving per 10 minutes (g / 10 min). I10 is measured in accordance with ASTM D 1238, Condition 190°C / 10 kg, and is reported in grams dissolving per 10 minutes (g / 10 min).

[0055] Mobile Die Rheometer (MDR) Testing

[0056] 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 designated as "ML," expressed in deciNewton-meters (dN-m). As curing or crosslinking progresses, the measured torque value increases, eventually reaching a maximum torque value. The maximum or highest measured torque value is designated 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 and 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 reaches 90% of the way from ML to MH, the faster the test specimen cures. Conversely, the longer the T90 crosslinking time, i.e., the longer it takes for the torque value to achieve 90% of the path from ML to MH, the slower the cure rate of the test sample.

[0057] Nuclear magnetic resonance ( 1 H NMR)

[0058] As used herein, the terms "nuclear magnetic resonance" or "nuclear magnetic resonance, NMR" or "proton NMR" refer to the spectral analysis of a material or compound that provides information about its chemical composition and structure. Approximately 50 mg of sample was dissolved in 0.7 mL of CDCl3 at room temperature to give a homogeneous solution. 1H spectra were acquired at room temperature on a Bruker 400 MHz (1H frequency) spectrometer. A 5 mm BBFO probe was used. Chemical shifts are given in parts per million (ppm) relative to tetramethylsilane (TMS) and are referenced to the residual signal of the protonated solvent (CDCl3, δ 7.26 ppm). The relaxation delay was set to 15 seconds for 16 scans.

[0059] Approximately 200 mg of sample was dissolved in 0.6 mL of deuterated chloroform containing 0.025 M chromium(III) acetylacetonate (Cr(acac)3) to give a homogeneous solution. 13 The C spectrum is 100.6MHz 13 Spectroscopy was performed at room temperature on a Bruker AVANCE III 400 MHz spectrometer operating at the C resonance frequency. A 5 mm BBFO probe was used. Chemical shifts are given in parts per million (ppm) relative to tetramethylsilane (TMS) and referenced to the residual signal of the protonated solvent (CDCl3: δC 77 ppm). Inverse gated decoupling was used to quantitatively 13 The pulse program for C NMR was used, with the relaxation delay set to 10 seconds for 4000 scans.

[0060] A sample solution of approximately 40% (v / v) in deuterated chloroform (CDCl3) containing chromium(III) acetylacetonate (Cr(acac)3) was prepared in a 16mm silicone-free NMR tube. The concentration of Cr(acac)3 in the sample solution was approximately 0.02M. The purpose of adding Cr(acac)3 was to act as a T1 relaxation reagent, improving the rate at which repetitive pulses could be acquired. The prepared sample solution was observed as a clear, homogeneous purple solution, the purple color being due to Cr(acac)3. 16mm silicone-free switchable13 C / 29 on an Agilent Mercury 400 FT-NMR spectrometer equipped with a Si probe. 29 Si NMR spectra were acquired at room temperature. Inverse gated decoupling was used to quantitatively 29 The pulse program for Si NMR was used, with the relaxation delay set to 13 seconds for 1000 scans. 29 For Si NMR experiments, tetramethylsilane (TMS) was used as an external reference.

[0061] Water tree growth test method: Measured in accordance with 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 of translucent thermoplastic or crosslinked electrical insulating materials to water tree growth. It is particularly applicable to extruded polymeric insulating materials useful in medium-voltage power cables. Ten compression-molded disc specimens, each containing a controlled conical defect, are subjected to an applied voltage of 5 kilovolts (kV) at 1 kilohertz (kHz) and 23°C ± 2°C for 30 days in a conductive aqueous solution of 0.01 Normal sodium chloride. The controlled conical 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-plane 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 microscopically and used to calculate a ratio defined as resistance to water tree growth. Water tree length (WTL) is the percentage of the insulation thickness through which water trees are growing. The lower the WTL value, the better the water tree resistance. WTL is reported as a percentage (%). DETAILED DESCRIPTION OF THE INVENTION

[0062] 1. Crosslinkable composition The present disclosure provides a composition. In one embodiment, the composition is a crosslinkable composition and includes an ethylene-based polymer, a polyaminosiloxane (PAS), and optionally a peroxide. The polyaminosiloxane has a structure of formula (I): Formula (I) [ka] (In the formula, R is a C6-C 20 is an aminoalkyl group, Si is a silicon atom, O is an oxygen atom, Z is a hydrogen atom or a C1-C 10 is a hydrocarbonyl group, q, m, and n each independently represent an integer of 2 to 1,000,000; 1 / 2 represents the end block structure of formula (II), [ka] 2 / 2 represents the linear structure of formula (III), [ka] 3 / 2 represents the branched structure of formula (IV). Formula (IV) [ka]

[0063] The present disclosure provides compositions that are crosslinkable compositions. A "crosslinkable composition," as used herein, is a composition containing an ethylene-based polymer and one or more additives (e.g., a free-radical initiator or an organic peroxide) 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-cure"), the crosslinkable composition crosslinks and becomes a "crosslinked composition" that contains an ethylene-based polymer that is structurally and physically distinct from the crosslinkable composition.

[0064] 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"), or medium-density polyethylene ("MDPE"), and combinations thereof. The crosslinkable composition contains 50% to 99%, or 80% to 99%, or 90% to 99%, or 95% to 99% by weight of the ethylene-based polymer, based on the total weight of the crosslinkable composition.

[0065] In one embodiment, the ethylene-based polymer is an ethylene / C-C 20 ethylene / C3-C6 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; 20 α-olefin copolymers or ethylene / C4-C8 α-olefin copolymers. 20 Non-limiting examples of α-olefins include propene, butene, 4-methyl-1-pentene, hexene, octene, decene, dodecene, tetradecene, hexadecene, and octadecene. α-olefins may also have cyclic structures, such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinylcyclohexane. Suitable ethylene / C3-C 20Non-limiting examples of α-olefin copolymers include ethylene / propylene copolymers, ethylene / butene copolymers, ethylene / hexene copolymers, and ethylene / octene copolymers.

[0066] In one embodiment, the ethylene-based polymer comprises a non-conjugated diene comonomer. Suitable non-conjugated diene monomers can be 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 astetrahydroin. polycyclic alicyclic fused and bridged ring dienes such as 5-methylene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene; and 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, and 5-vinyl-2-norbornene.

[0067] In one embodiment, the ethylene-based polymer is an ethylene / propylene / diene terpolymer (or "EPDM"). Non-limiting examples of suitable dienes are 1,4-hexadiene ("HD"), 5-ethylidene-2-norbornene ("ENB"), 5-vinylidene-2-norbornene ("VNB"), 5-methylene-2-norbornene ("MNB"), or dicyclopentadiene ("DCPD"). The diene content of the EPDM is 0.1 wt.% to 10.0 wt.%, or 0.2 wt.% to 5.0 wt.%, or 0.3 wt.% to 3.0 wt.%, based on the total weight of the EPDM.

[0068] 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 wherein R1 is a C1-C4 hydrocarbonyl group; R2 is a C1-C2 hydrocarbonyl group.

[0069] Non-limiting examples of suitable R groups include unsubstituted C1-C4 alkyl groups and unsubstituted C2-C4 alkenyl groups, including methyl, ethyl, propyl, butyl, ethenyl, propenyl, and butenyl groups. The unsubstituted C1-C4 alkyl groups and unsubstituted C2-C4 alkenyl groups can be branched or linear. In one embodiment, the R group is an unsubstituted linear C1-C4 alkyl group or an unsubstituted C2 alkenyl group, including, for example, methyl, ethyl, propyl, butyl, or ethenyl. In a further embodiment, the R group is selected from methyl, ethyl, butyl, and ethenyl. In one embodiment, the R group is selected from methyl, ethyl, and linear butyl groups.

[0070] Non-limiting examples of suitable R groups include unsubstituted C1-C2 alkyl groups and unsubstituted C2 alkenyl groups, including methyl, ethyl, and ethenyl groups. In one embodiment, the R group is selected from methyl and unsubstituted ethene groups.

[0071] In one embodiment, the ethylene-based polymer is (i) one or more hydrolyzable silyl groups, each hydrolyzable silyl group independently having the formula (R 2 ) m (R 3 ) 3-m a hydrolyzable silyl group, each R 2 are independently H, HO-, (C-C)alkoxy, (C-C)carboxy, phenoxy, (C-C alkyl-phenoxy, ((C-C)N-, (C-C alkyl(H)C=NO-, or ((C-C) alkyl)C=NO-, each R 3 is independently (C1-C6) alkyl or phenyl; (ii) C3-C 40 α-olefin comonomers, and (iii) Both (i) and (ii). Each R 2 may be free of H and HO—, or free of phenoxy and (C1-C9) alkylphenoxy. 2 may independently be (C-C)alkoxy, (C-C)carboxy, ((C-C)alkyl)N—, (C-C)alkyl(H)C═NO—, or ((C-C)alkyl)C═NO—, or (C-C)alkoxy, or (C-C)carboxy, or ((C-C)N—, or (C-C)alkyl(H)C═NO—, or ((C-C))alkylC═NO.

[0072] In one embodiment, the ethylene-based polymer is a low density polyethylene (LDPE) homopolymer having one, some, or all of the following properties: (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

[0073] The crosslinkable composition includes a polyaminosiloxane. As used herein, a "polyaminosiloxane" is a condensation product of one or more aminoalkylsilane precursors that are hydrolyzed in the presence of water at elevated temperatures (60-100°C) and subsequently subjected to condensation to form polysiloxane linkages, -Si-O-Si-, between the aminoalkylsilane precursor units. In this manner, a polyaminosiloxane is a chain of many (i.e., "poly") aminoalkylsilane precursors bonded together by -Si-O-Si- bonds. Polyaminosiloxanes (interchangeably referred to as "PAS") have the structure of formula (I): [ka] (In the formula, R is a C6-C 20 is an aminoalkyl group, Si is a silicon atom, O is an oxygen atom, Z is a hydrogen atom or a C1-C 10 is a hydrocarbonyl group, q is an integer of 2 to 1,000,000, or q is an integer of 5 to 100; m is an integer of 2 to 1,000,000, or m is an integer of 20 to 300; n is an integer from 2 to 1,000,000, or n is an integer from 10 to 700; 1 / 2 represents the end block structure of formula (II), [ka] 2 / 2 represents the linear structure of formula (III), [ka] 3 / 2 represents the branched structure of formula (IV). [ka]

[0074] The PAS having the structure of formula (I) is a C6-C 20 It includes R, an aminoalkyl group. The aminoalkyl group contains one or more nitrogen atoms (N) and can be a primary amino group and / or a secondary amino group. C6-C 20 The phenyl portion of the aminoalkyl group has the following structure (B): [ka] In the formula, R is a hydrocarbonyl group or an aminoalkyl group.

[0075] Non-limiting examples of aminoalkylsilane precursors suitable for the preparation of PAS of formula (I) include (phenylaminomethyl)methyldimethoxysilane (CAS: 17890-10-7), (aminoethylaminomethyl)phenethyltrimethoxysilane (CAS: 74113-77-2), p-aminophenyltrimethoxysilane (CAS: 33976-43-1), 3-(2,4-dinitrophenylamino)propyltriethoxysilane (CAS: 71783-41-0), n-phenylaminomethyltriethoxysilane (CAS: 77855-01-1), and n-phenylaminomethyltriethoxysilane (CAS: 77855-01-1). -73-3), n-phenylaminopropyltrimethoxysilane (CAS: 3068-76-6), m-aminophenyltrimethoxysilane (CAS: 70411-42-6), aminophenyltrimethoxysilane (CAS: 33976-43-1 / 70411-42-6), 3-(n-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride (CAS: 34937-00-3), 4-(trimethoxysilylethyl)benzyltrimethylammonium chloride, and combinations thereof.

[0076] In one embodiment, the aminoalkylsilane precursor is selected from n-phenylaminopropyltrimethoxysilane (CAS: 3068-76-6) and aminophenyltrimethoxysilane (CAS: 33976-43-1).

[0077] In one embodiment, the aminoalkylsilane precursor is phenylaminopropyltrimethoxysilane (CAS: 3068-76-6).

[0078] In one embodiment, the aminoalkylsilane precursor is aminophenyltrimethoxysilane (CAS: 33976-43-1).

[0079] The crosslinkable composition comprises 0.05 wt % to 3 wt %, or 0.1 wt % to 2.5 wt %, or 0.5 wt % to 2.0 wt % of the polyaminosiloxane, based on the total weight of the crosslinkable composition.

[0080] In addition to the ethylene-based polymer and PAS, 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, containing carbon, hydrogen, and two or more oxygen atoms and having 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. The crosslinkable composition includes, based on the total weight of the crosslinkable composition, greater than 0 wt. % to less than 2 wt. %, or 0.1 wt. % to 1.9 wt. %, or 0.2 wt. % to 1.8 wt. % of peroxide. It is understood that the ensemble of ethylene-based polymer, polyaminosiloxane, and peroxide makes up 100% by weight of the crosslinkable composition.

[0081] Organic peroxides have the formula R O -OOR O wherein each R O are independently (C1~C 20 ) alkyl group or (C6-C 20 ) aryl group. Each (C1-C 20 ) alkyl groups are independently unsubstituted or contain one or two (C-C 12 ) substituted with an aryl group. 20 The aryl group is unsubstituted or contains one to four (C-C 10 ) alkyl group. Alternatively, the organic peroxide may be a group of formula R O -OOROOR O wherein R is a diperoxide of (C-C 10 ) alkylene, (C3-C 10 ) a divalent hydrocarbon group such as cycloalkylene or phenylene, and each R O is as defined above.

[0082] 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), hydroxy)diisopropylbenzene, t-butylperoxy-2-ethylhexyl-monocarbonate, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethyl-2,5-dihydroxyperoxide, t-butylcumyl peroxide, 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 (ethylperoxy)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(α-t-butyl-peroxyisopropyl)benzene ("BIPB"), isopropyl alcohol, Examples of the isopropyl cumyl t-butyl peroxide include 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, butyl 4,4-di(tert-butylperoxy)valerate, and di(isopropyl cumyl) peroxide.

[0083] 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).

[0084] The crosslinkable composition of the present invention may include one or more optional additives. When additives are present, non-limiting examples of suitable additives include antioxidants, scorch retarders, coagents (e.g., triallyl isocyanurate, triallyl trimellitate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethyl acrylate, ethoxylated bisphenol A dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, N,N,N',N',N'',N''-hexaallyl-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.

[0085] In one embodiment, the crosslinkable composition comprises 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 LOWINOX TBM-6), 2,2'-thiobis(6-t-butyl-4-methylphenol (CAS No. 90-66-4, commercially available LOWINOX TBM-6), and 2,2'-thiobis(6-t-butyl-4-methylphenol) (CAS No. 90-66-4, commercially available 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 No. 6683-19-8), 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid 2,2'-thiodiethanediyl ester (e.g., IRGANOX 1035, CAS No. 41484-35-9), distearyl thiodipropionate ("DSTDP"), dilauryl thiodipropionate (e.g., IRGANOX PS 800), stearyl 3-(3,5-di-tert-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-methyiphenoi) (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,Examples of antioxidants include 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 wt.% to 1.5 wt.%, or 0.05 wt.% to 1.2 wt.%, or 0.07 wt.% to 1.0 wt.%, or 0.1 wt.% to 0.5 wt.%, based on the total weight of the crosslinkable composition.

[0086] In one embodiment, the crosslinkable composition comprises: 80% to 99% by weight, or 90% to 99% by weight, of an ethylene-based polymer; 0.1% by weight to 2.0% by weight, or 0.3% by weight to 1.0% by weight of polyaminosiloxane (PAS), and and from greater than 0 wt.% to less than 2 wt.%, or from 0.5 wt.% to 1.9 wt.% of peroxide, where the weight percent is based on the total weight of the crosslinkable composition, it being understood that the ethylene-based polymer, PAS, and peroxide collectively equal 100 wt.% of the crosslinkable composition.

[0087] 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) at a temperature of 120°C to 180°C to melt the ethylene-based polymer. The PAS (and optional additives such as antioxidants) are fed into the mixing device and melt-mixed with the ethylene-based polymer. The mixed compound (hereinafter referred to as the "PAS-PE compound") consisting of the ethylene-based polymer and the PAS (and optional additives) is collected and chopped into small pieces.

[0088] The PAS-PE compound and free radical initiator are mixed by placing pieces of the PAS-PE compound and peroxide (and optionally antioxidant(s)) in a container. The container is then shaken, rotated, tumbled, or otherwise agitated so that the peroxide is held in contact with the PAS-PE compound pieces or is otherwise absorbed by the PAS-PE compound pieces. The process involves heating the mixture of PAS-PE compound and peroxide at a temperature of 60°C, 70°C, or 80°C to 90°C or 100°C, or otherwise above the melting temperature of the peroxide. The mixture is heated for a period of 1 minute, 10 minutes, or 30 minutes to 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or 8 hours, thereby allowing the peroxide to diffuse into the PAS-PE compound pellets.

[0089] In one embodiment, the mixing and heating are performed sequentially.

[0090] In one embodiment, the mixing and heating occur simultaneously.

[0091] The peroxide-containing PAS-PE strips are cured (i.e., "crosslinked") by heating at a cure temperature of 100°C, or 110°C, or greater than 125°C to 150°C, or 180°C, or 200°C for a period of 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, PAS, and optional additives. The crosslinked composition is structurally and physically distinct from the crosslinkable composition.

[0092] 2. Crosslinked composition In one embodiment, a crosslinked composition is provided. The crosslinked composition includes an ethylene-based polymer, a polyaminosiloxane (PAS), and optional additives. The polyaminosiloxane (PAS) has the formula (I): [ka] (In the formula, R is a C6-C 20 is an aminoalkyl group, Si is a silicon atom, O is an oxygen atom, Z is a hydrogen atom or a C1-C 10 is a hydrocarbonyl, q is an integer of 2 to 1,000,000, or q is an integer of 5 to 100; m is an integer of 2 to 1,000,000, or m is an integer of 20 to 300; n is an integer from 2 to 1,000,000, or n is an integer from 10 to 700; 1 / 2 represents the end block structure of formula (II), [ka] 2 / 2 represents the linear structure of formula (III), [ka] 3 / 2 represents the branched structure of formula (IV). [ka]

[0093] The ethylene-based polymer in the crosslinked composition can be any of the ethylene-based polymers in the crosslinkable compositions disclosed hereinabove. In one embodiment, the ethylene-based polymer composition of the crosslinked composition is an 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.

[0094] The polyaminosiloxane (PAS) of formula (I) present in the crosslinked composition is the polymerization reaction product of aminoalkylsilane precursors. Non-limiting examples of aminoalkylsilane precursors suitable for producing the PAS of formula (I) include (phenylaminomethyl)methyldimethoxysilane (CAS: 17890-10-7), (aminoethylaminomethyl)phenethyltrimethoxysilane (CAS: 74113-77-2), p-aminophenyltrimethoxysilane (CAS: 33976-43-1), 3-(2,4-dinitrophenylamino)propyltriethoxysilane (CAS: 71783-41-0), n-phenylaminomethyltriethoxysilane (CAS: 77855- -73-3), n-phenylaminopropyltrimethoxysilane (CAS: 3068-76-6), m-aminophenyltrimethoxysilane (CAS: 70411-42-6), aminophenyltrimethoxysilane (CAS: 33976-43-1 / 70411-42-6), 3-(n-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride (CAS: 34937-00-3), 4-(trimethoxysilylethyl)benzyltrimethylammonium chloride, and combinations thereof.

[0095] In one embodiment, the polyaminosiloxane (PAS) of formula (I) is the polymerization reaction product of an aminoalkylsilane precursor selected from n-phenylaminopropyltrimethoxysilane (CAS: 3068-76-6) and aminophenyltrimethoxysilane (CAS: 33976-43-1).

[0096] In one embodiment, the polyaminosiloxane (PAS) of formula (I) is the polymerization reaction product of the aminoalkylsilane precursor phenylaminopropyltrimethoxysilane (CAS: 3068-76-6).

[0097] In one embodiment, the polyaminosiloxane (PAS) of formula (I) is the polymerization reaction product of the aminoalkylsilane precursor aminophenyltrimethoxysilane (CAS: 33976-43-1).

[0098] 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 wt. % to 1.0 wt. %, or 0.1 wt. % to 0.9 wt. %, or 0.3 wt. % to 0.9 wt. % of a PAS of formula (I), and The crosslinked composition has an average WTL of 3% to 12%, or 5% to 10%. In a further embodiment, the PAS of Formula (I) is the polymerization product of phenylaminopropyltrimethoxysilane (CAS: 3068-76-6). In yet a further embodiment, the PAS of Formula (I) is the polymerization product of aminophenyltrimethoxysilane (CAS: 33976-43-1). It is understood that the ensemble of the ethylene-based polymer, the PAS of Formula (I), and optional additives makes up 100% by weight of the crosslinked composition.

[0099] The crosslinked composition of the present invention may contain one or more optional additives. When an additive is present in the crosslinked composition, the additive may be any additive such as the additive in the crosslinkable composition disclosed herein above.

[0100] Purpose

[0101] 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, and combinations thereof.

[0102] By way of example and not limitation, several embodiments of the present disclosure will now be detailed in the following examples. [Example]

[0103] The materials used in the examples are described in Table 1 below. [Table 1]

[0104] 1. Preparation of polyaminosiloxane (PAS) 20 g of PAPTMS was added to a 100 mL round-bottom flask, then 20 mL of water was added, and the mixture was stirred for 7 days at 80° C. The water was removed to obtain polyaminosiloxane 1 (PAS1) having formula (I).

[0105] 20 g of p-APTMS was added to a 100 mL round-bottom flask, followed by 20 mL of water, and the mixture was stirred for 7 days at 80° C. The water was removed to obtain polyaminosiloxane 2 (PAS2) having formula (I).

[0106] The properties of PAS1 and PAS2 are shown in Table 2 below. [Table 2] * 29 The q / m / n ratio calculated from Si NMR was calculated as (RSi(OZ)O 1 / 2 ), (RSi(OZ)O 2 / 2 ) and (RSiO 3 / 2 ) peak areas were integrated and then ratio normalized.

[0107] 2.Composition LDPE1 pellets were fed into a Brabender mixer at a set temperature of 160°C and a rotor speed of 10 rpm. Antioxidants and ingredient(s) were fed into the polymer melt at set temperatures to form individual samples with different ingredient(s) from Table 1. Final mixing was performed for 4 minutes at the set temperature and a rotor speed of 45 rpm. The compound was collected and cut into small pieces for use.

[0108] 3. Pelletization The compound samples were fed into the hopper of a Brabender monolithic 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.

[0109] 4.Soaking A 250 mL fluorinated HDPE bottle was applied and sealed with 50 g of pellets and 0.865 g of DCP. The bottle was tightly sealed. Immersion was carried out at 70°C for 8 hours. The bottle was shaken every 0, 2, 5, 10, 20, and 30 minutes during the immersion process. The DCP-immersed pellets (XLPE pellets) were stored in the fluorinated bottle for testing after the immersion process.

[0110] 5. 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 sheets of 2 mm PET film. The sample and PET film were placed in the mold. The mold was then sandwiched between the upper and lower plates of a hot press and held at 120°C for 10 minutes under 0 MPa pressure for the preheating period. The temperature was heated from 120°C to 180°C within 7 minutes at 10 MPa for curing. 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 eight times, the mold was held at 180°C and 10 MPa for 13 minutes for curing. 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 3 below provides the composition and properties of each individual sample. [Table 3] CS = Comparative Sample IE = Inventive Example

[0111] Table 3 shows that the water tree lengths (WTL) of IE1-4 are shorter than those of CS1-3. IE1-4 have WTLs ranging from 5.3% to 9.9%, compared to the WTLs of CS1-3, which range from 13.55 to 28.08%, indicating improved water tree retardation for IE1-4 compared to CS1-3. Notably, although CS2 has more than twice the amount of conventional water tree retarder (2.00 wt% PDMS) compared to the amount of water tree retarder in IE1-4 (0.3-0.9 wt% PAS1 or PAS2), CS2 has a WTL value of 13.55%, which is greater than the WTLs of IE1-4, 5.3% to 9.9%.

[0112] The present disclosure is not limited to the embodiments and examples contained herein, but is expressly intended to include portions of the embodiments and modified forms of those embodiments, including combinations of elements of different embodiments, to the extent that they fall within the scope of the following claims. The present invention includes the following aspects. Section 1. 1. A crosslinkable composition comprising: an ethylene-based polymer; Polyaminosiloxane (PAS) having formula (I) [ka] (In the formula, R is a C6-C 20 is an aminoalkyl group, Si is a silicon atom, O is an oxygen atom, Z is a hydrogen atom or a C1-C 10 is a hydrocarbonyl group, q, m, and n each independently represent an integer of 2 to 1,000,000; 1 / 2 represents the end block structure of formula (II), [ka] 2 / 2 represents the linear structure of formula (III), [ka] 3 / 2 represents a branched structure of formula (IV) [ka] and, A crosslinkable composition, optionally comprising a peroxide. Section 2. the ethylene-based polymer has a density of 0.91 g / cc to 0.93 g / cc; Item 2. The crosslinkable composition according to Item 1, having a melt index of 0.5 g / 10 min to 5.0 g / 10 min. Section 3. 80% by weight to 99% by weight of the ethylene-based polymer; 0.05% by weight to 3% by weight of the polyaminosiloxane; Item 3. The crosslinkable composition according to any one of items 1 and 2, comprising more than 0% by weight and less than 2% by weight of a peroxide. Section 4. Item 4. The crosslinkable composition according to any one of items 1 to 3, further comprising an additive selected from the group consisting of antioxidants, scorch retarders, coagents, nucleating agents, processing aids, extender oils, carbon black, nanoparticles, UV stabilizers, and combinations thereof. Section 5. 1. A crosslinked composition comprising: an ethylene-based polymer; Polyaminosiloxane (PAS) having formula (I) [ka] (In the formula, R is a C6-C 20 is an aminoalkyl group, Si is a silicon atom, O is an oxygen atom, Z is a hydrogen atom or a C1-C 10 is a hydrocarbonyl group, q, m, and n each independently represent an integer of 2 to 1,000,000; 1 / 2 represents the end block structure of formula (II), [ka] 2 / 2 represents the linear structure of formula (III), [ka] 3 / 2 represents a branched structure of formula (IV). [ka] Section 6. the ethylene-based polymer has a density of 0.91 g / cc to 0.93 g / cc; Item 6. The crosslinked composition according to Item 5, having a melt index of 0.5 g / 10 min to 5.0 g / 10 min. Section 7. Item 5 to 6, comprising an additive selected from the group consisting of antioxidants, scorch retarders, coagents, nucleating agents, processing aids, extender oils, carbon black, nanoparticles, UV stabilizers, and combinations thereof. The crosslinked composition according to any one of items 5 to 6, further comprising an additive selected from the group consisting of antioxidants, scorch retarders, coagents, nucleating agents, processing aids, extender oils, carbon black, nanoparticles, UV stabilizers, and combinations thereof. Section 8. 90% by weight to 99% by weight of the ethylene-based polymer; and 0.1 wt % to 1.0 wt % of the PAS, Item 8. The crosslinked composition according to any one of items 5 to 7, wherein the crosslinked composition has an average WTL of 3% to 12%. Section 9. Item 9. The crosslinked composition according to item 8, wherein the PAS of formula (I) is a polymerization reaction product of phenylaminopropyltrimethoxysilane. Section 10. Item 9. The crosslinked composition according to item 8, wherein the PAS of formula (I) is a polymerization reaction product of aminophenyltrimethoxysilane.

Claims

1. 1. A crosslinkable composition comprising: an ethylene-based polymer; Polyaminosiloxane (PAS) having formula (I) 【Chemistry 1】 (In the formula, R is a C having a phenyl moiety ６ -C ２０ an aminoalkyl group or an aminophenyl group, Si is a silicon atom, O is an oxygen atom, Z is a hydrogen atom or C １ -C １０ is a hydrocarbonyl group, q, m, and n are each independently an integer from 2 to 1,000,000; 1 / 2 represents an endblock structure of formula (II), 【Chemistry 2】 2 / 2 represents a linear structure of formula (III), 【Transformation 3】 3 / 2 represents a branched structure of formula (IV) 【Chemistry 4】 and, A crosslinkable composition, optionally comprising a peroxide.

2. the ethylene-based polymer having a density of 0.91 g / cc to 0.93 g / cc; 2. The crosslinkable composition of claim 1, having a melt index of 0.5 g / 10 min to 5.0 g / 10 min as measured in accordance with ASTM D1238, condition 190° C. / 2.16 kg.

3. 80% to 99% by weight of the ethylene-based polymer; 0.05% to 3% by weight of the polyaminosiloxane; The crosslinkable composition according to any one of claims 1 to 2, comprising more than 0% by weight and less than 2% by weight of a peroxide.

4. 4. The crosslinkable composition of any one of claims 1 to 3, comprising an additive selected from the group consisting of antioxidants, scorch retarders, nucleating agents, processing aids, extender oils, carbon black, nanoparticles, UV stabilizers, and combinations thereof.

5. 1. A crosslinked composition comprising: an ethylene-based polymer; Polyaminosiloxane (PAS) having formula (I) 【Transformation 5】 (In the formula, R is a C having a phenyl moiety ６ -C ２０ an aminoalkyl group or an aminophenyl group, Si is a silicon atom, O is an oxygen atom, Z is a hydrogen atom or C １ -C １０ is a hydrocarbonyl group, q, m, and n are each independently an integer from 2 to 1,000,000; 1 / 2 represents an endblock structure of formula (II), 【Transformation 6】 2 / 2 represents a linear structure of formula (III), 【Transformation 7】 3 / 2 represents a branched structure of formula (IV). 【Transformation 8】

6. the ethylene-based polymer having a density of 0.91 g / cc to 0.93 g / cc; 6. The crosslinked composition of claim 5, having a melt index of 0.5 g / 10 min to 5.0 g / 10 min as measured in accordance with ASTM D1238, Condition 190° C. / 2.16 kg.

7. 7. The crosslinked composition of any one of claims 5 to 6, comprising an additive selected from the group consisting of antioxidants, scorch retarders, nucleating agents, processing aids, extender oils, carbon black, nanoparticles, UV stabilizers, and combinations thereof.

8. 90% to 99% by weight of the ethylene-based polymer; 0.1 wt % to 1.0 wt % of the PAS; The crosslinked composition of any one of claims 5 to 7, wherein the crosslinked composition has an average WTL of 3% to 12% as measured according to ASTM D6097-01a.

9. 9. The crosslinked composition of claim 8, wherein the PAS of formula (I) is a polymerization reaction product of phenylaminopropyltrimethoxysilane.

10. 9. The crosslinked composition of claim 8, wherein the PAS of formula (I) is a polymerization reaction product of aminophenyltrimethoxysilane.

11. The crosslinked composition according to any one of claims 5 to 8, comprising at least one of 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"-hexaallyl-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, and pentavinylpentamethylcyclopentasiloxane.

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