Reduced shrink polymeric compositions

Abstract

A polymeric composition includes 60 wt% to 94 wt% of an ethylene-based polymer based on a total weight of the polymeric composition. The ethylene-based polymer has a density of 0.885 g / cc to 0.93 g / cc as measured according to ASTM D792. The polymeric composition also includes 1 wt% to 30 wt% of a polymeric shrink additive based on a total weight of the polymeric composition. The polymeric shrink additive has a melting peak temperature or glass transition temperature greater than a melting peak temperature of the ethylene-based polymer and 0.5 wt% to 10 wt% of a compatibilizer based on a total weight of the polymeric composition.

Description

[0001] REDUCED SHRINK POLYMERIC COMPOSITIONS

[0002] BACKGROUND

[0003] Field of the disclosure

[0004] The present disclosure relates to polymeric compositions, and more specifically to reduced shrink polymeric compositions.

[0005] Introduction

[0006] There has been increased demand for broadband to connect data centers, office spaces and homes in view of the rise of the 5G network. The broadband industry is shifting towards the use of optical fibers over traditional copper wire as optical fibers offer the highest data transmission efficiency and reliability. Accompanying the shift to optical fiber use is fiber densification which is the increase in the number of fibers present in a data cable.

[0007] The jacketing of optical fibers can shrink which is not desirable. Optical fibers may suffer from data transmission quality loss and / or signal attenuation when exposed to mechanical stresses. For example, shrinking of the jacket positioned on and around the fiber may induce mechanical stresses that cause signal attenuation. Shrinkage of the jacket may appear soon after extrusion (i.e., “Post Extrusion Shrinkage”) and as the jacket experiences temperature cycles during its use (i.e., “Cyclic Shrinkage”). Typical Cyclic Shrinkage values of polyethylene are about 2.5% or greater. To reduce stress in the fiber, the polymeric composition forming the jacket should exhibit a Post Extrusion Shrinkage value of 0.5% or less as measured according to the PES Test provided below. Further, the polymeric composition should exhibit a Cyclic Shrinkage of 2.20% or less. Low shrink fibers have been attempted, including those that comprise polypropylene. See United States Patent number 4,948,669. Polypropylene is known to have a low shrink (e.g., about 0.5% or less), but typically requires high weight percent loading (e.g., greater than 50 vol%) in polymeric compositions in order to have shrink properties approach that of polypropylene.

[0008] In view of the foregoing, it would be surprising to discover a polymeric composition that can exhibit a Post Extrusion Shrinkage value of 0.5% or less and a Cyclic Shrinkage of 2.20% or less without experiencing a substantial decrease in mechanical properties. SUMMARY OF THE DISCLOSURE

[0009] The inventors of the present application have discovered a polymeric composition that can exhibit a Post Extrusion Shrinkage value of 0.5% or less and a Cyclic Shrinkage of 2.20% or less without experiencing a substantial decrease in mechanical properties.

[0010] The invention is the result of discovering that Post Extrusion Shrinkage and Cyclic Shrinkage can be reduced by including a polymeric shrink additive having a melting peak temperature or glass transition temperature greater than a melting peak temperature than ethylenic components of the polymeric composition. Without being bound by theory, it is believed that during polymeric composition extrusion the high shear stresses stretch and orient polyethylene chains which are then subsequently frozen in place during post-extrusion cooling. When the polymeric composition is subsequently exposed to elevated temperatures during use, the aligned polymer chains gain enough mobility to relax thereby leading to macroscopic shrinkage. It is believed that inclusion of the polymeric shrink additive functions similar to a filler which maintains a distinct phase within the polymeric composition. The distinct phase of the shrink additive resists the relaxation of the polymeric chains and thus reduces shrinkage because the polymeric shrink additive’s greater melting peak temperature or glass transition temperature means its polymeric chains are not mobile while the ethylenic components’ chains are mobile.

[0011] According to a first feature of the present disclosure, a polymeric composition, comprises 60 wt% to 94 wt% of an ethylene-based polymer based on a total weight of the polymeric composition, wherein the ethylene-based polymer has a density of 0.885 g / cc to 0.93 g / cc as measured according to ASTM D792; 1 wt% to 30 wt% of a polymeric shrink additive based on a total weight of the polymeric composition, wherein the polymeric shrink additive has a melting peak temperature or glass transition temperature greater than a melting peak temperature of the ethylene-based polymer; and 0.5 wt% to 10 wt% of a compatibilizer based on a total weight of the polymeric composition.

[0012] According to another feature of the present disclosure, the polymeric composition comprises from 70 wt% to 94 wt% of the ethylene-based polymer based on a total weight of the polymeric composition.

[0013] According to another feature of the present disclosure, the ethylene-based polymer may have having any one of features (i) to (vi): (i) the ethylene-based polymer is linear or substantially linear; (ii) the ethylene-based polymer has a density of 0.91 g / cc to 0.93 g / cc as measured according to ASTM D792: (iii) the ethylene-based polymer has a melting peak temperature of 110°C to 130°C as measured according to Differential Scanning Calorimetry; (iv) the ethylene-based polymer is a copolymer of ethylene and butene; (v) the ethylene-based polymer has a melt index of 0.3 g / lOmin. to 1.0 g / lOmin. as measured according to ASTM D1238; and (vi) any combination of two or more of features (i) to (v).

[0014] According to another feature of the present disclosure, wherein the polymeric shrink additive is selected from any one of (i) to (iii): (i) a cyclic olefin copolymer; (ii) a polypropylene-based polymer; and (iii) a combination of (i) and (ii).

[0015] According to another feature of the present disclosure, the polymeric shrink additive is the cyclic polyolefin copolymer and has any one features (i) to (v): (i) the cyclic polyolefin copolymer is a copolymer of ethylene and norbomene; (ii) the cyclic polyolefin copolymer is a copolymer of ethylene and from 50 wt% to 90 wt% cyclic comonomer based on the total weight of the cyclic polyolefin copolymer; (iii) the cyclic polyolefin copolymer has a glass transition temperature of 135°C to 200°C as measured according to Differential Scanning Calorimetry; (iv) the cyclic polyolefin has a density of 0.95 g / cc to 1.10 g / cc as measured according to ASTM D792; and (v) any combination of two or more of features (i) to (iv).

[0016] According to another feature of the present disclosure, the polymeric shrink additive is the polypropylene-based polymer and has any one features (i) to (iii): (i) the polypropylene- based polymer is 90 wt% or greater propylene based on the total weight of the polypropylene- based polymer; (ii) the polypropylene-based polymer has a melting peak temperature of 135 °C to 200° as measured according to Differential Scanning Calorimetry; (iii) the polypropylene- based polymer has a density of 0.89 g / cc to 0.92g / cc as measured according to ASTM D792; and (iv) any combination of two or more of features (i) to (iii).

[0017] According to another feature of the present disclosure, the compatibilizer is an ethylenepropylene copolymer.

[0018] According to another feature of the present disclosure, the polymeric composition comprises 5 wt% to 20 wt% of the polymeric shrink additive based on the total weight of the polymeric composition.

[0019] According to another feature of the present disclosure, the polymeric composition exhibits any one of features (i) to (vi): (i) a Post Extrusion Shrinkage of 0.50 or less as measured according to the PES Test; (ii) a Cyclic Shrinkage of 2.2 or less as measured according to the CS Test; (iii) a density of 0.94 g / cc to 0.98 g / cc as measured according to ASTM D792; (iv) a melt index of 0.5 g / lOmin. to 2.0 g / 10min.; (v) an ESCR of 2000 hours or greater as measured according to ASTM D1693-15 in 10% Igepal; and (vi) a combination of any two of (i) to (iv). According to another feature of the present disclosure, a cable, comprises: a conductor; and the polymeric composition positioned around the conductor.

[0020] DETAILED DESCRIPTION

[0021] As used herein, the term “and / or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and / or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.

[0022] All ranges include endpoints unless otherwise stated.

[0023] Test methods refer to the most recent test method as of the priority date of this document unless a date is indicated with the test method number as a hyphenated two-digit number. References to test methods contain both a reference to the testing society and the test method number. Test method organizations are referenced by one of the following abbreviations: ASTM refers to ASTM International (formerly known as American Society for Testing and Materials); 1EC refers to International Electrotechnical Commission; EN refers to European Norm; DIN refers to Deutsches Institut fur Normung; and ISO refers to International Organization for Standards.

[0024] As used herein, the term weight percent (“wt%”) designates the percentage by weight a component is of a total weight of the polymeric composition unless otherwise specified.

[0025] Melt index (h) values herein refer to values determined according to ASTM method D1238 at 190 degrees Celsius (°C) with 2.16 Kilogram (kg) mass and are provided in units of grams eluted per ten minutes (“g / 10 min”).

[0026] Density values herein refer to values determined according to ASTM D792 at 23 °C and are provided in units of grams per cubic centimeter (“g / cc”).

[0027] As used herein, Chemical Abstract Services registration numbers (“CAS#”) refer to the unique numeric identifier as most recently assigned as of the priority date of this document to a chemical compound by the Chemical Abstracts Service. Polymeric composition

[0028] The present disclosure is directed to a polymeric composition. The polymeric composition comprises an ethylene-based polymer, a shrink additive and a compatibilizer.

[0029] The polymeric composition may exhibit one or more of the following features (i) to (vi): (i) a Post Extrusion Shrinkage of 0.50 or less as measured according to the PES Test, (ii) Cyclic Shrinkage of 2.20 or less as measured according to the CS Test; (iii) a density of 0.94 g / cc to 0.98 g / cc as measured according to ASTM D792; (iv) a melt index (E) of 0.5 g / 10 min. to 2.0 g / 10min.; (v) an environmental stress cracking resistance (“ESCR”) of 2000 hours or greater as measured according to ASTM D1693-15 in 10% Igepal; and (vi) a combination of any two of (i) to (v).

[0030] The polymeric composition may exhibit a Post Extrusion Shrinkage of 0.50 or less as measured according to the PES Test. For example, the polymeric composition may exhibit a Post Extrusion Shrinkage of 0.50 or less, or 0.45 or less, or 0.40 or less, or 0.35 or less, or 0.30 or less, or 0.25 or less, or 0.20 or less, or 0.15 or less, or 0.11 or less, while at the same time, 0.10 or greater, or 0.20 or greater, or 0.30 or greater, or 0.40 or greater as measured according to the PES Test.

[0031] The polymeric composition may exhibit a Cyclic Shrinkage of 2.20 or less as measured according to the CS Test. For example, the polymeric composition may exhibit a Cyclic Shrinkage of 2.20 or less, or 2.10 or less, or 2.00 or less, or 1.90 or less, or 1.80 or less, or 1.70 or less, or 1.60 or less, or 1.50 or less, or 1.40 or less, or 1.30 or less, or 1.20 or less, or 1.10 or less, or 1.80 or less, or 1.00 or less, or 0.90 or less, or 0.80 or less, or 0.70 or less, or 0.60 or less, or 0.50 or less, or 0.40 or less, or 0.30 or less, while at the same time, 0.20 or greater, or 0.50 or greater, or 1.00 or greater, or 1.50 or greater, or 2.00 or greater as measured according to the CS Test.

[0032] The polymeric composition may exhibit a density of 0.90 g / cc to 0.94 g / cc as measured according to ASTM D792. For example, the polymeric composition may have a density of 0.900 g / cc or greater, or 0.905 g / cc or greater, or 0.910 g / cc or greater, or 0.915 g / cc or greater, or 0.920 g / cc or greater, or 0.925 g / cc or greater, or 0.930 g / cc or greater, or 0.935 g / cc or greater, while at the same time, 0.940 g / cc or less, or 0.935 g / cc or less, or 0.930 g / cc or less, or 0.925 g / cc or less, or 0.920 g / cc or less, or 0.915 g / cc or less, or 0.910 g / cc or less, or 0.905 g / cc or less as measured according to ASTM D792.

[0033] The polymeric composition may have a melt index (I2) of 0.5 g / 10 min to 2.0 g / 10 min. as measured according to ASTM D1238. For example, the ethylene-based polymer may have a melt index (I2) of 0.5 g / 10 min or greater, or 0.6 g / 10 min or greater, or 0.7 g / 10 min or greater, or 0.8 g / 10 min or greater, or 0.9 g / 10 min or greater, or 1.0 g / 10 min or greater, or 1.1 g / 10 min or greater, or 1.2 g / 10 min or greater, or 1.3 g / 10 min or greater, or 1.4 g / 10 min or greater, or 1.5 g / 10 min or greater, or 1.6 g / 10 min or greater, or 1.7 g / 10 min or greater, or 1.8 g / 10 min or greater, or 1.9 g / 10 min or greater, while at the same time, 2.0 g / 10 min or less, or

[0034] 1.9 g / 10 min or less, or 1.8 g / 10 min or less, or 1.7 g / 10 min or less, or 1.6 g / 10 min or less, or

[0035] 1.5 g / 10 min or less, or 1.4 g / 10 min or less, or 1.3 g / 10 min or less, or 1.2 g / 10 min or less, or

[0036] 1.1 g / 10 min or less, or 1.0 g / 10 min or less, or 0.9 g / 10 min or less, or 0.8 g / 10 min or less, or

[0037] 0.7 g / 10 min or less, or 0.6 g / 10 min or less as measured according to ASTM DI 238.

[0038] The polymeric composition may have an ESCR of 2000 hours or greater as measured according to ASTM D1693-15 in 10% Igepal. For example, the polymeric composition may have an ESCR of 2000 hours or greater, or 2500 hours or greater, or 3000 hours or greater, or 3500 hours or greater, or 4000 hours or greater, or 4500 hours or greater, or 5000 hours or greater as measured according to ASTM D1693-15 in 10% Igepal.

[0039] Ethylene-based polymer

[0040] As noted above, the composition may comprise the ethylene-based polymer. The ethylene-based polymer may have any of features (i) to (vi): (i) the ethylene-based polymer is linear or substantially linear; (ii) the ethylene-based polymer has a density of 0.950 g / cc or less as measured according to ASTM D792; (iii) the ethylene-based polymer has a melting peak temperature of 110°C to 130°C as measured according to Differential Scanning Calorimetry; (iv) the ethylene-based polymer is a copolymer of ethylene and butene; (v) the ethylene-based polymer has a melt index of 0.3 g / lOmin. to 1.0 g / 10min.; and (vi) any combination of two or more of features (i) to (v).

[0041] As used herein, “ethylene -based” polymers are polymers in which greater than 50 wt% of the monomers are ethylene though other co-monomers may also be employed. Ethylenebased polymers include ethylene and one or more C3-C20 a-olefin comonomers such as propylene, 1 -butene, 1 pentene, 4-methyl-l -pentene, 1 -hexene, and 1 -octene. In a specific example, the ethylene-based polymer is a copolymer of ethylene and hexene. In another example, the ethylene-based polymer may be a copolymer of ethylene and butene.

[0042] The ethylene -based polymer may comprise 50 wt% or greater, 60 wt% or greater, 70 wt% or greater, 80 wt% or greater, 85 wt% or greater, 90 wt% or greater, or 91 wt% or greater, or 92 wt% or greater, or 93 wt% or greater, or 94 wt% or greater, or 95 wt% or greater, or 96 wt% or greater, or 97 wt% or greater, or 97.5 wt% or greater, or 98 wt% or greater, or 99 wt% or greater, while at the same time, 99.5 wt% or less, or 99 wt% or less, or 98 wt% or less, or 97 wt% or less, or 96 wt% or less, or 95 wt% or less, or 94 wt% or less, or 93 wt% or less, or 92 wt% or less, or 91 wt% or less, or 90 wt% or less, or 85 wt% or less, or 80 wt% or less, or 70 wt% or less, or 60 wt% or less of ethylene monomers as measured using Nuclear Magnetic Resonance (NMR) or Fourier- Transform Infrared (FTIR) Spectroscopy.

[0043] Other units of ethylene-based polymers may be derived from one or more polymerizable monomers including, but not limited to, polar monomers such as unsaturated esters. The unsaturated esters (i.e. polar monomers) may be alkyl acrylates, alkyl methacrylates, or vinyl carboxylates. The alkyl groups can have from 1 to 8 carbon atoms, or from 1 to 4 carbon atoms. The carboxylate groups can have from 2 to 8 carbon atoms, or from 2 to 5 carbon atoms. Examples of acrylates and methacrylates include, but are not limited to, ethyl acrylate, methyl acrylate, methyl methacrylate, t-butyl acrylate, n-butyl acrylate, n-butyl methacrylate, and 2 ethylhexyl acrylate. Examples of vinyl carboxylates include, but are not limited to, vinyl acetate, vinyl propionate, and vinyl butanoate. The ethylene-based polymer may have a polar comonomer content of 40 wt% or less, or 35 wt% or less, or 30 wt% or less, or 25 wt% or less, or 20 wt% or less, 15 wt%, or 10 wt%, or 5 wt% or less, or 3 wt% or less, or 1 wt% or less, or 0 wt% based on the total weight of the ethylene-based polymer as measured using Nuclear Magnetic Resonance (NMR) or Fourier-Transform Infrared (FTIR) Spectroscopy.

[0044] The ethylene-based polymer can have a unimodal or a multimodal molecular weight distribution and can be used alone or in combination with one or more other types of ethylenebased polymers (e.g., a blend of two or more ethylene-based polymers that differ from one another by monomer composition and content, catalytic method of preparation, molecular weight, molecular weight distributions, densities, etc.). If a blend of ethylene-based polymers is employed, the polymers can be blended by any in-reactor or post-reactor process. The term “multimodal polymer” refers to polymers that are characterized by having at least two distinct peaks in a gel permeation chromatography (GPC) chromatogram depicting the molecular weight distribution of the composition. Accordingly, the generic term multimodal polymer includes bimodal polymers, which have two primary fractions: a first fraction, which may be a low molecular weight fraction and / or component, and a second fraction, which may be a high molecular weight fraction and / or component.

[0045] The polymeric composition may comprise from 60 wt% to 94 wt% of the ethylenebased polymer based on a total weight of the polymeric composition. For example, the polymeric composition may comprise from 60 wt% or greater, or 65 wt% or greater, or 70 wt% or greater, or 75 wt% or greater, or 80 wt% or greater, or 85 wt% or greater, or 90 wt% or greater, or 92 wt% or greater, while at the same time, 94 wt% or less, or 90 wt% or less, or 85 wt% or less, or 80 wt% or less, or 75 wt% or less, or 70 wt% or less, or 65 wt% or less of the ethylene-based polymer based on a total weight of the polymeric composition.

[0046] The ethylene-based polymer may have short-chain branching and as such may be classified as linear or substantially linear. As here used, “substantially linear” means that the bulk polymer is substituted, on average, with about 0.01 long-chain branches / 1000 total carbons (including both backbone and branch carbons) to about 3 long-chain branches / 1000 total carbons, preferably from about 0.01 long-chain branches / 1000 total carbons to about 1 long-chain branch / 1000 total carbons, more preferably from about 0.05 long-chain branches / 1000 total carbons to about 1 long-chain branch / 1000 total carbons, and especially from about 0.3 long chain branches / 1000 total carbons to about 1 long chain branches / 1000 total carbons. “Long-chain branches” or “long-chain branching” (LCB) means a chain length of at least one (1) carbon less than the number of carbons in the comonomer, as opposed to “short chain branches” or “short chain branching” (SCB) which means a chain length two (2) less than the number of carbons in the comonomer. For example, an ethylene / 1 -octene substantially linear polymer has backbones with long chain branches of at least seven (7) carbons in length, but it also has short chain branches of only six (6) carbons in length, whereas an ethylene / l-hexene substantially linear polymer has long chain branches of at least five (5) carbons in length but short chain branches of only four (4) carbons in length. LCB can be distinguished from SCB by using13C nuclear magnetic resonance (NMR) spectroscopy and to a limited extent, e.g. for ethylene homopolymers, it can be quantified using the method of Randall (Rev. Macromol. Chem. Phys., C29 (2&3). P.285-297). However, as a practical matter, current13C NMR spectroscopy cannot determine the length of a long-chain branch in excess of about six (6) carbon atoms and as such, this analytical technique cannot distinguish between a seven (7) and a seventy (70) carbon branch. The LCB can be about as long as about the same length as the length of the polymer backbone.

[0047] The ethylene-based polymer has a density of 0.885 g / cc to 0.93 g / cc as measured according to ASTM D792. For example, the ethylene-based polymer has a density of 0.885 g / cc or greater, or 0.89 g / cc or greater, or 0.90 g / cc or greater, or 0.91 g / cc or greater, or 0.92 g / cc or greater, while at the same time, 0.93 g / cc or less, or 0.92 g / cc or less, or 0.91 g / cc or less, or 0.90 g / cc or less, or 0.89 g / cc or less as measured according to ASTM D792.

[0048] The ethylene-based polymer has a melting peak temperature of 110°C to 130°C as measured according to Differential Scanning Calorimetry. For example, the ethylene-based polymer has a melting peak temperature of 110°C or greater, or 112°C or greater, or 114°C or greater, 116°C or greater, or 118°C or greater, 120°C or greater, or 122°C or greater, 124°C or greater, or 126°C or greater, 128°C or greater, while at the same time, 130°C or less, or 128°C or less, or 126°C or less, or 124°C or less, or 122°C or less, or 120°C or less, or 118°C or less, or 116°C or less, or 114°C or less, or 112°C or less as measured according to Differential Scanning Calorimetry.

[0049] The ethylene-based polymer may have a melt index (I2) of 0.3 g / 10 min to 1.0 g / 10 min. as measured according to ASTM DI 238. For example, the ethylene-based polymer may have a melt index (I2) of 0.3 g / 10 min or greater, or 0.4 g / 10 min or greater, or 0.5 g / 10 min or greater, or 0.6 g / 10 min or greater, or 0.7 g / 10 min or greater, or 0.8 g / 10 min or greater, or 0.9 g / 10 min or greater, while at the same time, 1.0 g / 10 min or less, or 0.9 g / 10 min or less, or 0.8 g / 10 min or less, or 0.7 g / 10 min or less, or 0.6 g / 10 min or less, or 0.5 g / 10 min or less, or 0.4 g / 10 min or less, or 0.3 g / 10 min or less, or 0.2 g / 10 min or less as measured according to ASTM D1238.

[0050] Polymeric shrink additive

[0051] The polymeric composition comprises the polymeric shrink additive. The addition of the polymeric shrink additive causes the polymeric composition to exhibit both a lower post extrusion shrink and a lower cyclic shrink. According to various examples, the polymeric shrink additive has a melting peak temperature or glass transition temperature greater than a melting peak temperature of the ethylene-based polymer.

[0052] The polymeric composition comprises from 1 wt% to 30 wt% of the polymeric shrink additive based on a total weight of the polymeric composition. For example, the polymeric composition comprises 1 wt% or greater, or 5 wt% or greater, or 10 wt% or greater, or 15 wt% or greater, or 20 wt% or greater, or 25 wt% or greater, while at the same time, 30 wt% or less, or 25 wt% or less, or 20 wt% or less, or 15 wt% or less, or 10 wt% or less, or 5 wt% or less, or 2 wt% or less of the polymeric shrink additive based polymer based on a total weight of the polymeric composition. In a specific example, the polymeric composition comprises from 20 wt% to 50 wt% of the polymeric shrink additive based polymer based on a total weight of the polymeric composition

[0053] The polymeric shrink additive is selected from a cyclic polyolefin copolymer, a polypropylene-based polymer, and combinations thereof. In examples where the polymeric shrink additive is a cyclic polyolefin copolymer, the cyclic polyolefin copolymer may have any one features (i) to (v): the cyclic polyolefin copolymer is a copolymer of ethylene and a cyclic comonomer such as norbomene; (ii) the cyclic polyolefin copolymer is a copolymer of ethylene and from 50 wt% to 90 wt% cyclic comonomer based on the total weight of the cyclic polyolefin copolymer; (iii) the cyclic polyolefin has a glass transition temperature of 135°C to 200°C as measured according to Differential Scanning Calorimetry; (iv) the cyclic polyolefin has a density of 0.95 g / cc to 1.10 g / cc as measured according to ASTM D792; and (v) any combination of two or more of features (i) to (iv).

[0054] The cyclic polyolefin copolymer examples of the is a copolymer of an olefin and one or more cyclic moieties. For example, the cyclic polyolefin copolymer may comprise an olefin (e.g., ethylene, propylene, butene, hexene, octene, etc.) and a cyclic comonomer such as norbornene, cyclopentene, other cyclic comonomers, and combinations thereof. The cyclic polyolefin copolymer may comprise 50 wt% or greater, 60 wt% or greater, 70 wt% or greater, 80 wt% or greater, 85 wt% or greater, while at the same time, 90 wt% or less, or 85 wt% or less, or 80 wt% or less, or 70 wt% or less, or 60 wt% or less of cyclic comonomers based on the total weight of the cyclic polyolefin copolymer as measured using Nuclear Magnetic Resonance (NMR) or Fourier- Transform Infrared (FTIR) Spectroscopy.

[0055] In cyclic olefin copolymer examples, the shrink additive will have a glass transition temperature greater than the melting peak temperature of the ethylene-based polymer. The cyclic polyolefin copolymer may have a glass transition temperature of 135 °C to 200°C as measured according to Differential Scanning Calorimetry. For example, the cyclic polyolefin copolymer may have a glass transition temperature of 135°C or greater, or 140°C or greater, or 145°C or greater, 150°C or greater, or 155°C or greater, or 160°C or greater, or 165°C or greater, or 170°C or greater, or 175°C or greater, or 180°C or greater, or 185°C or greater, or 190°C or greater, 195°C or greater, while at the same time, 200°C or less, or 195°C or less, or 190°C or less, or 185°C or less, or 180°C or less, or 175°C or less, or 170°C or less, or 165°C or less, or 160°C or less, or 155°C or less, or 150°C or less, or 145°C or less, or 140°C or less as measured according to Differential Scanning Calorimetry.

[0056] The cyclic polyolefin copolymer may have a density of 0.95 g / cc to 1.10 g / cc as measured according to ASTM D792. For example, the cyclic polyolefin copolymer may have a density of 0.95 g / cc or greater, or 0.96 g / cc or greater, or 0.97 g / cc or greater, or 0.98 g / cc or greater, or 0.99 g / cc or greater, or 1.00 g / cc or greater, or 1.01 g / cc or greater, or 1.02 g / cc or greater, or 1.03 g / cc or greater, or 1.04 g / cc or greater, or 1.05 g / cc or greater, or 1.06 g / cc or greater, or 1.07 g / cc or greater, or 1.08 g / cc or greater, or 1.09 g / cc or greater, while at the same time, 1.10 g / cc or less, or 1.09 g / cc or less, or 1.08 g / cc or less, or 1.07 g / cc or less, or 1.06 g / cc or less, or 1.05 g / cc or less, or 1.04 g / cc or less, or 1.03 g / cc or less, or 1.02 g / cc or less, or 1.01 g / cc or less, or 1.00 g / cc or less, or 0.99 g / cc or less, or 0.98 g / cc or less, or 0.97 g / cc or less, or 0.96 g / cc or less as measured according to ASTM D792.

[0057] The polymeric shrink additive may additionally or alternatively be a polypropylene- based polymer. In polypropylene-based polymer, the shrink additive will have a melting peak temperature greater than the melting peak temperature of the ethylene-based polymer. As used herein, “propylene-based” polymers are polymers in which greater than 50 wt% of the monomers are propylene though other co-monomers may also be employed. Propylene-based polymers include ethylene and one or more C3-C20 a-olefin comonomers such as ethylene, 1 - butene, 1 pentene, 4-methyl-l -pentene, 1 -hexene, and 1 -octene. The propylene-based polymer may comprise 50 wt% or greater, 60 wt% or greater, 70 wt% or greater, 80 wt% or greater, 85 wt% or greater, 90 wt% or greater, or 91 wt% or greater, or 92 wt% or greater, or 93 wt% or greater, or 94 wt% or greater, or 95 wt% or greater, or 96 wt% or greater, or 97 wt% or greater, or 97.5 wt% or greater, or 98 wt% or greater, or 99 wt% or greater, while at the same time, 99.5 wt% or less, or 99 wt% or less, or 98 wt% or less, or 97 wt% or less, or 96 wt% or less, or 95 wt% or less, or 94 wt% or less, or 93 wt% or less, or 92 wt% or less, or 91 wt% or less, or 90 wt% or less, or 85 wt% or less, or 80 wt% or less, or 70 wt% or less, or 60 wt% or less of propylene monomers as measured using Nuclear Magnetic Resonance (NMR) or Fourier- Transform Infrared (FTIR) Spectroscopy.

[0058] The propylene-based polymer may have any of features (i) to (iv): (i) the polypropylene-based polymer is 90 wt% or greater propylene based on the total weight of polypropylene-based polymer; (ii) the polypropylene-based polymer has a melting peak temperature of 160°C to 200° as measured according to Differential Scanning Calorimetry; (iii) the polypropylene- based polymer has a density of 0.89 g / cc to 0.92g / cc as measured according to ASTM D792; and (iv) any combination of two or more of features (i) to (iii).

[0059] The polypropylene-based polymer has a melting peak temperature of 135 °C to 200° as measured according to Differential Scanning Calorimetry. For example, the polypropylene- based polymer has a melting peak temperature of or 135°C or greater, or 140°C or greater, or 145°C or greater, or 150°C or greater, or 155°C or greater, or 160°C or greater, or 165°C or greater, or 170°C or greater, or 175°C or greater, or 180°C or greater, or 185°C or greater, or 190°C or greater, or 195 °C or greater, while at the same time, 200°C or less, or 195 °C or less, or 190°C or less, or 185°C or less, or 180°C or less, or 175°C or less, or 170°C or less, or 165 °C or less, or 160°C or less, or 155°C or less, or 150°C or less, or 145°C or less, or 140°C or less as measured according to Differential Scanning Calorimetry. The polypropylene-based polymer may have a density of 0.89 g / cc to 0.92g / cc as measured according to ASTM D792. For example, the cyclic polyolefin may have a density of 0.890 g / cc or greater, or 0.895 g / cc or greater, or 0.900 g / cc or greater, or 0.905 g / cc or greater, or 0.910 g / cc or greater, or 0.915 g / cc or greater, while at the same time, 0.920 g / cc or less, or 0.915 g / cc or less, or 0.910 g / cc or less, or 0.905 g / cc or less, or 0.900 g / cc or less, or 0.895 g / cc or less as measured according to ASTM D792.

[0060] Compatibilizer

[0061] The polymeric composition may comprise a compatibilizer. The compatibilizer may be a random copolymer, a block copolymer or combinations thereof. The compatibilizer may comprise ethylene and one or more monomers such as an alpha olefin (e.g., a C3-C20 a-olefin comonomers such as propylene, 1 -butene, 1 pentene, 4-methyl- 1 -pentene, 1 -hexene, and 1- octene) as well as polar comonomers. Where applicable, the monomers of the compatibilizer may be isotactic, syndiotactic, atactic or combinations thereof across the polymer chain. The compatibilizer may be from 5 wt% ethylene to 95 wt% ethylene based on the total weight of the compatibilizer with the balance being one or more comonomers. For example, the compatibilizer may comprise 5 wt% or greater, or 10 wt% of greater, or 20 wt% or greater, or 30 wt% or greater, or 40 wt% or greater, or 50 wt% or greater, 60 wt% or greater, 70 wt% or greater, 80 wt% or greater, 85 wt% or greater, 90 wt% or greater, while at the same time, 95 wt% or less, or 90 wt% or less, or 80 wt% or less, or 70 wt% or less, or 60 wt% or less, or 50 wt% or less, or 40 wt% or less, or 30 wt% or less, or 20 wt% or less, or 10 wt% or less of ethylene monomers as measured using Nuclear Magnetic Resonance (NMR) or Fourier- Transform Infrared (FTIR) Spectroscopy with the balance being one or more comonomers.

[0062] The polymeric composition may comprise from 0.5 wt% to 10 wt% of the compatibilizer based on the total weight of the polymeric composition. For example, the polymeric composition may comprise 0.5 wt% or greater, or 1 wt% or greater, or 2 wt% or greater, or 3 wt% or greater, or 4 wt% or greater, or 5 wt% or greater, or 6 wt% or greater, or 7 wt% or greater, or 8 wt% or greater, or 9 wt% or greater, while at the same time, 10 wt% or less, or 9 wt% or less, or 8 wt% or less, or 7 wt% or less, or 6 wt% or less, or 5 wt% or less, or 4 wt% or less, or 3 wt% or less, or 2 wt% or less, or 1 wt% or less of the compatibilizer based on the total weight of the polymeric composition. Additives

[0063] The polymeric composition may comprise additional additives in the form of antioxidants, cross-linking co-agents, cure boosters and scorch retardants, processing aids, coupling agents, ultraviolet stabilizers (including UV absorbers), antistatic agents, additional nucleating agents, slip agents (i.e., silicone gums), lubricants, viscosity control agents, tackifiers, anti-blocking agents, surfactants, extender oils, acid scavengers, anti-drip agents (e.g., ethylene vinyl acetate) and metal deactivators. The polymeric composition may comprise from 0.01 wt% to 20 wt% of one or more of the additional additives.

[0064] The UV light stabilizers may comprise hindered amine light stabilizers (“HALS”) and UV light absorber (“UVA”) additives. Representative UVA additives include benzotriazole types such as TINUVIN 326™ light stabilizer and TINUVIN 328™ light stabilizer commercially available from BASF, Inc. Blends of HAL’s and UVA additives are also effective.

[0065] The antioxidants may comprise hindered phenols such as tetrakis[methylene(3,5-di- tert-butyl-4-hydroxyhydro-cinnamate)]methane; bis[(beta-(3,5-ditert-butyl-4-hydroxybenzyl) methylcarboxyethyl)]-sulphide, 4,4’-thiobis(2-methyl-6-tert-butylphenol), 4,4’-thiobis(2-tert- butyl-5-methylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), and thiodiethylene bis(3,5- di-tert-butyl-4-hydroxy)-hydrocinnamate; phosphites and phosphonites such as tris(2,4-di-tert- butylphenyl)phosphite and di-tert-butylphenyl-phosphonite; thio compounds such as dilaurylthiodipropionate, dimyristylthiodipropionate, and distearylthiodipropionate; various siloxanes; polymerized 2.2.4-trimethyl-l,2-dihydroquinoline, n,n’-bis(l,4-dimethylpentyl-p- phenylenediamine), alkylated diphenylamines, 4,4’-bis(alpha, alpha- dimethylbenzyl)diphenylamine, diphenyl-p-phenylenediamine, mixed di-aryl-p-phenylenediamines, and other hindered amine anti-degradants or stabilizers.

[0066] The processing aids may comprise metal salts of carboxylic acids such as zinc stearate or calcium stearate; fatty acids such as stearic acid, oleic acid, or erucic acid; fatty amides such as stearamide, oleamide, erucamide, or N,N'-ethylene bis-stearamide; polyethylene wax; oxidized polyethylene wax; polymers of ethylene oxide; copolymers of ethylene oxide and propylene oxide; vegetable waxes; petroleum waxes; non-ionic surfactants; silicone fluids, polysiloxanes, fluoropolymers, and / or fluoroelastomers.

[0067] Compounding

[0068] The components of the polymeric composition can be added to a batch or continuous mixer for melt blending. The components can be added in any order or first preparing one or more masterbatches for blending with the other components. The melt blending may be conducted at a temperature above the highest melting polymer but lower than the maximum compounding temperature of 285 °C. The melt-blended composition can then either be delivered to an extruder or an injection-molding machine or passed through a die for shaping into the desired article, or converted to pellets, tape, strip or film or some other form for storage or to prepare the material for feeding to a next shaping or processing step. Optionally, if shaped into pellets or some similar configuration, then the pellets, etc. can be coated with an anti -block agent to facilitate handling while in storage.

[0069] Examples of compounding equipment that may be used include internal batch mixers, continuous single or twin-screw mixers, or kneading continuous extruders. The type of mixer utilized, and the operating conditions of the mixer, will affect properties of the composition such as viscosity, volume resistivity, and extruded surface smoothness.

[0070] Cable

[0071] The polymeric composition may be utilized in a cable. In some examples, the cable may be a coated conductor. In other examples, the cable may be a fiber optic cable. In coated conductor examples, the coated conductor includes a conductor and a coating on the conductor, the coating including the polymeric composition. The polymeric composition is at least partially positioned around the conductor to produce the coated conductor. The conductor may comprise a conductive metal or an optically transparent structure.

[0072] In optical fiber cable examples, the cable comprises a conductor and the polymeric composition is positioned around the conductor. The polymeric composition may be in the form of a buffer tube, one or more jacketing layers on the cable, and / or as other components in the cable. The conductor may include optical fibers or other transmissive components.

[0073] Examples

[0074] Materials

[0075] The following materials were used in the formation of the inventive examples (“IE”) and the comparative examples (“CE”).

[0076] LLDPE is a linear low density polyethylene having a butene comonomer, a density of 0.92 g / cc as measured according to ASTM D792, a melting peak temperature of 118°C as measured according to Differential Scanning Calorimetry, a melt index (L) of 0.65 g / lOmin. LLDPE is commercially available from The Dow Chemical Company, Midland, Michigan.

[0077] AO is Thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and is commercially available as SONGNOX™ 1035 from Songwon, Ulsan, Korea. PROP is propylene homopolymer having a melting peak temperature of 167°C, a density of 0.90 g / cc as measured according to ASTM D792 and is available from LyondellBasell, Houston, Texas.

[0078] COMP is a 50 wt% ethylene and 50 wt% isotactic propylene olefin block copolymer having a density of 0.904 g / cc as measured according to ASTM D792 and is commercially available from The Dow Chemical Company, Midland, Michigan.

[0079] Sample Preparation

[0080] Each of the samples was prepared by combing all listed material of the materials in Table 1, for each example, into the mixing bowl of a Brabender mixer with Banbury blades. The mixer was turned on and the materials were mixed at a temperature of 190°C to 220°C at 40 to 50 revolutions per minute. Compounds were pelletized and extruded on a copper conductor having a 1.651 millimeter diameter with 0.762 millimeter wall thickness using a Brabender mini wireline.

[0081] Test Methods

[0082] Differential Scanning Calorimetry: Differential Scanning Calorimetry (“DSC”) is performed on a TA Instruments Q2000 DSC using a 5 milligram sample that had been pressed into a film. The DSC was performed according to the following steps: equilibrate at 30.00°C; ramp up at 10.00°C per minute to 140.00°C; hold the temperature constant for 1.00 minute; ramp down at 10.00°C per minute to 0.00°C: hold the temperature constant 3.00 minutes: and ramp up at 10.00°C per minute to 180.00°C. The melting peak temperature is reported as the temperature at which peak enthalpy was reached.

[0083] PES Test: Extruded wires were first conditioned at room temperature for one day. A 122 cm long test specimen was prepared by stretching the copper conductor and removing the polymer jacket in a single piece. Post extrusion shrinkage was measured on cable jacket 24 hours after removing it from the conductor. Specimen length was measured using a caliper instrument with + / - 0.0005 inch resolution. The shrinkage is measured as the total contraction in length of the sample. Reported values are the average of five separate samples.

[0084] CS Test: The cyclic shrinkage was measured on the same cable jacket as the post extrusion test after the post extrusion shrinkage test. The CS test is performed by placing the jacket in an oven at 40°C and allowed to equilibrate for 20 minutes. The temperature is then ramped to 100°C at a rate of 0.5°C per minute. Once at 100°C, the jacket is allowed to equilibrate for 1 hour. The temperature is then reduced to back to 40°C at a rate of 0.5 °C per minute. The steps of equilibrating at 40°C, ramping temperature, equilibrating at 100°C and then cooling are repeated four more times. The reported shrinkage data is the average of five separate measurements, each on a different jacket.

[0085] Mechanical Testing: Type IV dog bone samples were die-cut out from the machine direction for tensile and elongation measurements per ASTMD638. Measurements were made on an Instron 4201 using 1001b load cell with a 2 in / min displacement rate. The average of five specimen is reported.

[0086] Brittleness: Low temperature brittleness was tested on 10 test specimens for each sample, according to ASTM D746. The test specimens were cut to strips of 0.25 + / - 0.02 in. wide, and 0.075 + / -0.005 in. thick using a customer die. The test specimens were then placed into holder and immersed into the LTB apparatus containing heat transfer media of methanol and liquid N2. The test specimens were conditioned at -76C for 6 minutes, then removed and examined while bending 90degrees in both directions looking for any splits or cracks.

[0087] Environmental Stress Cracking Resistance (ESCR): Materials Environmental Stress Crack Resistance was measured according to ASTM DI 693. Samples were compression molded into plaques, followed by die cutting into 38mm x 13mm specimens within 24 hours after the plaques were molded. Prior to testing, a controlled imperfection (notch) was made on one surface of each specimen. A total of 10 specimens were bent and loaded into a specimen holder which was placed into a test tube filled with a surface-active agent (Igepal CO-630) solution with a concentration of 10% in water. The tube was sealed and placed in a temperature- controlled bath at 50°C. Reported data corresponds to the testing time (hours) with 0 specimens have failed / cracked (F0).

[0088] Results

[0089] Table 1 provides the composition (wt%) and shrink performance of CE1-CE3 and IE1- IE8.

[0090] Table 1

[0091] As can be seen in Table 1, CE does exhibit a Post Extrusion Shrinkage value of 0.5% or less, but does not exhibit a Cyclic Shrinkage of 2.20% or less. Unlike CE, IE1-IE3 demonstrate a Post Extrusion Shrinkage value of 0.5% or less and a Cyclic Shrinkage of 2.20% or less when including the polymeric shrink additive. Advantageously, IE1-IE3 also do not exhibit reduced elongation, lowered ESCR or low temperature brittleness performance indicating that the polymeric shrink additive provides the above-noted advantages, but does not diminish other properties.

Claims

CLAIMSWhat is claimed is1. A polymeric composition, comprising:60 wt% to 94 wt% of an ethylene-based polymer based on a total weight of the polymeric composition, wherein the ethylene-based polymer has a density of 0.885 g / cc to 0.93 g / cc as measured according to ASTM D792;1 wt% to 30 wt% of a polymeric shrink additive based on a total weight of the polymeric composition, wherein the polymeric shrink additive has a melting peak temperature or glass transition temperature greater than a melting peak temperature of the ethylene-based polymer; and0.5 wt% to 10 wt% of a compatibilizer based on a total weight of the polymeric composition.

2. The polymeric composition of claim 1, wherein the polymeric composition comprises from 70 wt% to 94 wt% of the ethylene-based polymer based on a total weight of the polymeric composition.

3. The polymeric composition of any one of claims 1 and 2 having any one of features (i) to (vi):(i) the ethylene-based polymer is linear or substantially linear;(ii) the ethylene-based polymer has a density of 0.91 g / cc to 0.93 g / cc as measured according to ASTM D792;(iii) the ethylene-based polymer has a melting peak temperature of 110°C to 130°C as measured according to Differential Scanning Calorimetry;(iv) the ethylene-based polymer is a copolymer of ethylene and butene;(v) the ethylene-based polymer has a melt index of 0.3 g / lOmin. to 1.0 g / lOmin. as measured according to ASTM D1238; and(vi) any combination of two or more of features (i) to (v).

4. The polymeric composition of any one of claims 1-3, wherein the polymeric shrink additive is selected from any one of (i) to (iii):(i) a cyclic olefin copolymer;(ii) a polypropylene-based polymer; and(iii) a combination of (i) and (ii).

5. The polymeric composition of claim 4, wherein the polymeric shrink additive is the cyclic polyolefin copolymer and has any one features (i) to (v):(i) the cyclic polyolefin copolymer is a copolymer of ethylene and norbomene;(ii) the cyclic polyolefin copolymer is a copolymer of ethylene and from 50 wt% to 90 wt% cyclic comonomer based on the total weight of the cyclic polyolefin copolymer;(iii) the cyclic polyolefin copolymer has a glass transition temperature of 135°C to 200°C as measured according to Differential Scanning Calorimetry;(iv) the cyclic polyolefin has a density of 0.95 g / cc to 1.10 g / cc as measured according to ASTM D792; and(v) any combination of two or more of features (i) to (iv).

6. The polymeric composition of claim 4, wherein the polymeric shrink additive is the polypropylene-based polymer and has any one features (i) to (iii):(i) the polypropylene-based polymer is 90 wt% or greater propylene based on the total weight of the polypropylene-based polymer;(ii) the polypropylene-based polymer has a melting peak temperature of 135°C to 200° as measured according to Differential Scanning Calorimetry;(iii) the polypropylene-based polymer has a density of 0.89 g / cc to 0.92g / cc as measured according to ASTM D792; and(iv) any combination of two or more of features (i) to (iii).

7. The polymeric composition of any one of claims 1-6, wherein the compatibilizer is an ethylene-propylene copolymer.

8. The polymeric composition of any one of claims 1-7, wherein the polymeric composition comprises 5 wt% to 20 wt% of the polymeric shrink additive based on the total weight of the polymeric composition.

9. The polymeric composition of any one of claims 1-9 having any one of features (i) to(vi):(i) a Post Extrusion Shrinkage of 0.50 or less as measured according to the PES Test;(ii) a Cyclic Shrinkage of 2.2 or less as measured according to the CS Test;(hi) a density of 0.94 g / cc to 0.98 g / cc as measured according to ASTM D792;(iv) a melt index of 0.5 g / lOmin. to 2.0 g / lOmin;(v) an ESCR of 2000 hours or greater as measured according to ASTM DI 693- 15 in 10% Igepal; and(vi) a combination of any two of (i) to (iv).

10. A cable, comprising: a conductor; and the polymeric composition of any one of claims 1 to 9 positioned around the conductor.