SOLID CROSSLINKED POLYOLEFIN COMPOSITIONS FOR WIRE AND CABLE COATING

Abstract

The present disclosure provides a composition. In an embodiment, a crosslinked polymeric composition is provided and comprises (A) from 4 wt % to 45 wt % of a thermoplastic polymer, (B) from 52 wt % to 95 wt % of a moisture-curable polyolefin, and (C) from 0.05 wt % to 7 wt % of a moisture condensation catalyst. The present disclosure provides an article. In an embodiment, a coated conductor is provided and comprises a conductor, and a coating on the conductor. The coating comprises a crosslinked polymeric composition comprising (A) from 4 wt % to 45 wt % of a thermoplastic polymer, (B) from 52 wt % to 95 wt % of a moisture-curable polyolefin, and (C) from 0.05 wt % to 7 wt % of a moisture condensation catalyst.

Claims

1. A crosslinked polymeric composition comprising: (A) from 4 wt % to 45 wt % of a thermoplastic polymer; (B) from 52 wt % to 95 wt % of a moisture-curable polyolefin; and (C) from 0.05 wt % to 7 wt % of a moisture condensation catalyst.

2. The composition of claim 1 wherein the thermoplastic polymer comprises high density polyethylene.

3. The composition of claim 2 wherein the high density polyethylene has a density from 0.945 g/cm3 to 0.970 g/cm3 and a melt index from 0.5 g/10 min to 10 g/10 min.

4. The composition of claim 1 wherein the moisture-curable polyolefin has a density from 0.920 g/cm3 to 0.930 g/cm3 and a melt index from 0.5 g/10 min to 2.5 g/10 min.

5. The composition of claim 1 wherein the polymeric composition has a gel content from 60% to 80%.

6. The composition of claim 5 wherein the polymeric composition has a hot creep value from 10% to 45%.

7. The composition of claim 1 wherein the polymeric composition has a hot deformation value at 150° C. from 7% to 36%.

8. (canceled)

9. The composition of claim 3 comprising: from 5 wt % to 40 wt % of high density polyethylene; from 55 wt % to 90 wt % of the moisture-curable polyolefin; from 3 wt % to 7 wt % of the moisture condensation catalyst; a gel content from 60% to 80%; a hot creep value from 10% to 40%; and a hot deformation value from 7% to 36%.

10. (canceled)

11. (canceled)

12. (canceled)

13. A coated conductor comprising: a conductor; and a coating on the conductor, the coating comprising the crosslinked polymeric composition of claim 1.

14. (canceled)

15. The coated conductor of claim 9 comprising: a surface smoothness from 102 μ.Math.cm to 184 μ.Math.cm; a hot creep value from 10% to 40%; and a hot deformation value at 150° C. from 7% to 36%.

Description

DETAILED DESCRIPTION

[0044] The present disclosure provides a crosslinked polymeric composition. The crosslinked polymeric composition (interchangeably referred to as “the composition”), includes from 4 wt % to 45 wt % of a thermoplastic polymer, from 52 wt % to 95 wt % of a moisture-curable polyolefin, and from 0.05 wt % to 7 wt % of a moisture condensation catalyst.

Thermoplastic Polymer

[0045] The present composition includes a thermoplastic polymer such as a polyolefin, for example. In an embodiment, the thermoplastic polymer is an ethylene-based polymer. Nonlimiting examples of suitable ethylene-based polymers high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ethylene/α-olefin copolymer.

[0046] In an embodiment, the thermoplastic polymer is an HDPE. “High density polyethylene” or “HDPE,” is an ethylene-based polymer having a density from 0.940, or 0.950, or 0.960 to 0.970, or 0.980 grams per cubic centimeter (g/cm.sup.3). The HDPE can include a C.sub.3 to C.sub.20 α-olefin comonomer or a C.sub.4 to C.sub.8 α-olefin comonomer. The HDPE has a melt index from 0.5, or 1.0, or 3.0 to 5.0, or 8.0, or 10.0 grams per 10 minutes (g/10 min).

[0047] In an embodiment, the thermoplastic polymer is an HDPE that is an ethylene/C.sub.4 to C.sub.8 α-olefin copolymer having one, some, or all of the following properties:

[0048] (i) a density from 0.945 g/cm.sup.3 to 0.970 g/cm.sup.3; and/or

[0049] (ii) a melt index from 0.5 g/10 min, or 1.0 g/10 min, or 3.0 g/10 min to 8.0 g/10 min, or 10.0 g/10 min.

[0050] The composition includes the thermoplastic polymer in an amount from 4, or 5, or 8, or 10, or 15 to 20, or 25, or 30, or 35, or 40, or 45 wt %. In a further embodiment, the composition includes the thermoplastic polymer in an amount from 4 to 45 wt %, or from 5 to 45 wt %, or from 10 to 35 wt %, or from 15 to 20 wt %. Weight percentage of the thermoplastic polymer is based on the total weight of the composition.

[0051] The present disclosure contemplates use of a blend of two or more thermoplastic polymers disclosed herein. The blend may be two or more of the following thermoplastic polymers: HDPE, MDPE, LDPE and/or LLDPE. The blend may be two different HDPEs, for example.

[0052] The thermoplastic polymer may comprise two or more embodiments disclosed herein.

Moisture-Curable Polyolefin

[0053] The present composition includes a moisture-curable polyolefin. The moisture-curable polyolefin is a silyl polyolefin. The silyl polyolefin is a polyolefin comprising silane groups. The silane groups can be introduced through copolymerization reactions between an olefin and a silane or by grafting a silane onto a polyolefin as described, for example, in U.S. Pat. Nos. 3,646,155 and 6,048,935.

[0054] Grafting of the silane onto the polyolefin can be performed in the presence of a free radical initiator; or alternatively, with ionizing radiation. Nonlimiting examples of free radical initiators include peroxides and azo compounds. Peroxides suitable for use include dicumyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane, lauryl peroxide, and tert-butyl peracetate. A suitable azo compound is 2,2-azobisisobutyronitrile. In an embodiment, the amount of free radical initiator is from 0.001, or 0.005, or 0.01, or 0.03, or 0.05, or 0.07 to 0.08, or 0.1, or 0.15, or 0.3, or 0.5, or 1, or 1.5, or 2, or 3, or 5 parts per hundred resin (phr). In a further embodiment, the amount of free radical initiator is from 0.001 to 5 phr, or from 0.005 to 1 phr, or from 0.01 to 0.15, or from 0.03 to 0.1 phr. The term “resin” within “parts per hundred resin,” refers to the moisture-curable polyolefin described herein. In an embodiment, the weight ratio of the silane to the initiator is from 10:1, or 18:1 to 250:1, or 500:1. In a further embodiment, the weight ratio of the silane to the initiator is from 10:1 to 500:1, or from 18:1 to 250:1. Grafting of the silane onto the polyolefin can be performed by blending the free radical initiator in the first stage of a reactor extruder, such as a BUSS™ kneader. The melt temperature used during the grafting process can be from 160° C. to 260° C., or from 190° C. to 230° C., depending upon the residence time and the half-life of the free radical initiator.

[0055] Silanes suitable for use include unsaturated silanes that comprise (i) an ethylenically unsaturated hydrocarbyl group (e.g., vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or gamma-(meth)acryloxy allyl group); and (ii) a hydrolyzable group (e.g., hydrocarbyloxy group, hydrocarbonyloxy group, or hydrocarbylamino group). Nonlimiting examples of hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, and alkyl or arylamino groups.

[0056] In an embodiment, the silane is an unsaturated alkoxy silane (e.g., vinyl trimethoxy silane, vinyl triethoxy silane, vinyl triacetoxy silane and gamma-(meth)acryloxy propyl trimethoxy silane), such as disclosed along with methods of preparation in U.S. Pat. No. 5,266,627, which is incorporated by reference herein in its entirety.

[0057] Nonlimiting examples of silyl polyolefins suitable for use include those having the following formula:

##STR00001##

in which R.sub.1 is a hydrogen atom or methyl group; x and y are 0 or 1 with the proviso that when x is 1, y is 1; m and n are independently an integer from 0 to 12 inclusive, preferably 0 to 4, and each R″ independently is a hydrolyzable organic group such as an alkoxy group having from 1 to 12 carbon atoms (e.g., methoxy, ethoxy, butoxy), aryloxy group (e.g., phenoxy), araloxy group (e.g. benzyloxy), aliphatic acyloxy group having from 1 to 12 carbon atoms (e.g., formyloxy, acetyloxy, propanoyloxy), amino or substituted amino groups (e.g., alkylamino, arylamino), or a lower alkyl group having 1 to 6 carbon atoms inclusive, with the proviso that not more than one of the three R groups is an alkyl.

[0058] The silyl polyolefin may further comprise heat stabilizers, light stabilizers, and pigments.

[0059] Silyl polyolefins suitable for use include SI-LINK™ DFDA-5451 and DFDB-5451, which are copolymers of ethylene and vinyl trimethoxy silane commercially available from The Dow Chemical Company.

[0060] In an embodiment, the amount of silicon in the moisture-curable polyolefin is from 0.1, or 0.3, or 0.5, or 0.7, or 1, or 1.5, or 2 to 2.5. or 3, or 3.5, or 5, or 7 or 10, or 20 wt %. In a further embodiment, the amount of silicon in the moisture-curable polyolefin is from 0.1 to 20 wt %, or from 0.3 to 10 wt %, or from 0.7 to 5 wt % or from 0.5 to 3 wt %. The amount of silicon is based on the total weight of the moisture-curable polyolefin.

[0061] In an embodiment, the moisture-curable polyolefin has a density from 0.870, or 0.900, or 0.920 to 0.930, or 0.950, or 0.970 g/cm.sup.3. In a further embodiment, the moisture-curable polyolefin has a density from 0.870 to 0.970 g/cm.sup.3, or from 0.900, or 0.950 g/cm.sup.3 or from 0.920 to 0.930 g/cm.sup.3. In a particular embodiment, the moisture-curable polyolefin has a density of 0.922 g/cm.sup.3.

[0062] In an embodiment, the moisture-curable polyolefin has a melt index from 0.3, or 0.5, or 1, or 1.2, or 1.4 to 1.6, or 1.8, or 2, or 4, or 8, or 10, or 50 grams per 10 minutes (g/10 min). In a further embodiment, the moisture-curable polyolefin has a melt index from 0.3 to 50 g/10 min, or from 1.2 to 1.8 g/10 min, or from 1.4 to 1.6 g/10 min. In a particular embodiment, the moisture-curable polyolefin has a melt index of 1.5 g/10 min.

[0063] In an embodiment, the moisture-curable polyolefin is a silyl polyolefin that is a copolymer of ethylene and vinyl trimethoxysilane having one, some, or all of the following properties:

[0064] (i) a density from 0.920 to 0.930 g/cm.sup.3; and/or

[0065] (ii) a melt index from 0.5 g/10 min to 2.5 g/10 min.

[0066] In an embodiment, the composition includes the moisture-curable polyolefin in an amount from 52, or 53, or 55, or 60 to 70, or 75, or 85, or 90, or 95 wt %. In a further embodiment, the composition includes the moisture-curable polyolefin in an amount from 52 to 95 wt %, or from 55 to 95 wt %, or from 55 to 75 wt %, or from 60 to 70 wt %. Weight percentage of the moisture-curable polyolefin is based on the total weight of the composition.

[0067] The moisture-curable polyolefin may comprise two or more embodiments disclosed herein.

Moisture Condensation Catalyst

[0068] The moisture condensation catalyst (alternatively termed a crosslinking catalyst), suitable for use includes Lewis acids, Lewis bases, Brönsted acids, Brönsted bases and combinations thereof. Lewis acids are chemical species that can accept electrons from another chemical species. Lewis bases are chemical species that can donate electrons to another chemical species. Nonlimiting examples of moisture condensation catalysts suitable for use include (i) tin carboxylates such as dibutyl tin dilaurate (DBTDL), dimethyl hydroxy tin oleate, dioctyl tin maleate, di-n-butyl tin maleate, dibutyl tin diacetate, dibutyl tin dioctoate, stannous acetate, stannous octoate; (ii) organo-metal compounds such as lead naphthenate, zinc caprylate and cobalt naphthenate; and (iii) mineral acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid, sulfuric acid, sulfonic acid, boric acid and perchloric acid; and (iv) amines such as primary amines, secondary amines and tertiary amines. In an embodiment, the moisture condensation catalyst is DBTDL or sulfonic acid.

[0069] The moisture condensation catalyst is present during the process of melt blending the thermoplastic polymer and moisture-curable polyolefin. In an embodiment, the moisture condensation catalyst can be added to the thermoplastic polymer and/or moisture-curable polyolefin in the form of a masterbatch.

[0070] In an embodiment, the moisture condensation catalyst has a density from 0.88, or 0.90, or 0.91, or 0.93, or 0.95 to 0.97, or 0.99, or 1.0, or 1.2, or 1.45 or 1.6 g/cm.sup.3. In a further embodiment, the moisture condensation catalyst has a density from 0.88 to 1.6 g/cm.sup.3, or from 0.93 to 1.45 g/cm.sup.3.

[0071] In an embodiment, the moisture condensation catalyst has a melt index from 0.3, or 0.5, or 0.7, or 0.9, or 0.91, or 0.92 to 0.93, or 0.94, or 1, or 2, or 4, or 8, or 10 grams per 10 minutes (g/10 min). In a further embodiment, the moisture condensation catalyst has a melt index from 0.3 to 10 g/10 min, or from 0.9 to 4 g/10 min, or from 0.92 to 0.93 g/10 min.

[0072] Moisture condensation catalysts suitable for use include SI-LINK™ DFDA-5481, DFDB-5480, and DFDA-5488, which are masterbatch copolymers commercially available from The Dow Chemical Company.

[0073] In an embodiment, the composition includes the moisture condensation catalyst in an amount from 0.05, or 0.1, or 0.5, or 1, or 3, or 4 to 6, or 7 wt %. In a further embodiment, the composition includes the moisture condensation catalyst in an amount from 0.05 to 7 wt %, or from 3 to 7 wt %, or from 4 to 6 wt %. In a particular embodiment, the composition includes 5 wt % of the moisture condensation catalyst. Weight percentage of the moisture condensation catalyst is based on the total weight of the composition.

[0074] The moisture condensation catalyst may comprise two or more embodiments disclosed herein.

Fillers and Additives

[0075] The composition of the present disclosure can include an optional filler. In an embodiment, the filler has flame retardant properties. The filler may or may not interact and/or may or may not react with the moisture condensation catalyst. In a further embodiment, the filler is coated with a material (e.g., stearic acid), that will prevent or retard the filler from interfering with the silane/polyolefin crosslinking reaction. Nonlimiting examples of fillers suitable for use include kaolin clay, magnesium hydroxide, silica, calcium carbonate and carbon black, stearic acid and combinations thereof.

[0076] The amount of filler in the composition is less than would cause unacceptably large degradation of the mechanical and/or chemical properties of the composition. In an embodiment, the composition includes the filler in an amount from 0.1, or 0.5, or 1, or 2, or 5 to 8, or 10, or 20, or 35 wt %. In a further embodiment, the composition includes the filler in an amount from 0.1 to 35 wt %, or 0.5 to 8 wt %. Weight percentage of the filler is based on the total weight of the composition.

[0077] The filler may comprise two or more embodiments disclosed herein.

[0078] The composition of the present disclosure can include an optional additive. Nonlimiting examples of fillers suitable for use include antioxidants (e.g., hindered phenols such as IRGANOX™ 1010 available from Ciba Specialty Chemicals); phosphites (e.g., IRGAFOS™ 168 available from Ciba Specialty Chemicals); UV stabilizers; cling additives; light stabilizers (such as hindered amines); plasticizers (such as dioctylphthalate or epoxidized soy bean oil); metal deactivators; scorch inhibitors; mold release agents; tackifiers (such as hydrocarbon tackifiers); waxes (such as polyethylene waxes); nucleating agents; processing aids (such as oils, organic acids such as stearic acid, metal salts of organic acids); oil extenders (such as paraffin oil and mineral oil); colorants; and pigments. Moisture generators can accelerate the cure phase of the process during which crosslinks are created.

[0079] The composition of the present disclosure excludes the use of a foaming agent. In other words, the present composition is a non-foamed composition.

[0080] The amount of additive in the composition is less than would interfere with desired physical or mechanical properties of the composition and is determined by the skilled artisan. In an embodiment, the composition includes the additive in an amount from 0.1, or 0.5, or 1, or 2, or 5 to 8, or 10, or 20, or 35 wt %. In a further embodiment, the composition includes the additive in an amount from 0.1 to 35 wt %, or from 0.5 to 8 wt %. Weight percentage of the additive is based on the total weight of the composition.

[0081] The additive may comprise two or more embodiments disclosed herein.

Composition

[0082] In an embodiment, the composition has a sum weight of the thermoplastic polymer (TP) and the moisture-curable polyolefin (MCP) of 80, or 85, or 90, or 91, or 92, or 93, or 94 to 95, or 96, or 97, or 98 wt %. In a further embodiment, the composition has a sum weight of the TP and the MCP from 80 to 98 wt %, or from 90 to 97 wt %, or from 94 to 96 wt %. In a particular embodiment, the composition has a sum weight of the TP and the MCP of 95 wt %.

[0083] In an embodiment, the composition has a sum weight of the moisture-curable polyolefin (MCP) and the moisture condensation catalyst (MCC) of 50, or 60, or 70, or 75, or 80, or 85, or 90 to 95, or 97, or 98 wt %. In a further embodiment, the composition has a sum weight of the MCP and the MCC from 50 to 98 wt %, or from 60 to 95 wt %, or from 85 to 95 wt %.

[0084] In an embodiment, the composition comprises a weight ratio of the MCP to the TP from 1, or 1.4, or 2, or 3, or 3.8, or 4.5, or 5, or 5.3, or 7 to 8, or 8.5, or 9, or 15, or 18, or 20. In a further embodiment, the composition comprises a weight ratio of the MCP to the TP from 1 to 20, or from 3 to 18, or from 5 to 9.

[0085] In an embodiment, the composition comprises a weight ratio of the MCP to the MCC from 5, or 10, or 11, or 13, or 15, or 16 to 17, or 18, or 19, or 20, or 30. In a further embodiment, the composition comprises a weight ratio of the MCP to the MCC from 5 to 30, or from 10 to 20, or from 15 to 18.

[0086] In an embodiment, the composition comprises a weight ratio of the TP to the MCC from 0.5, or 1, or 2, or 3, or 4 to 5, or 6, or 7, or 8, or 10, or 20, or 30. In a further embodiment, the composition comprises a weight ratio of the TP to the MCC from 0.5 to 30, or from 1 to 10, or from 3 to 8.

[0087] Weight percentage of the additive is based on the total weight of the composition.

[0088] The composition of the present disclosure includes a polymeric component that comprises the thermoplastic polymer and the moisture-curable polyolefin. In an embodiment, the polymeric component is a crosslinked form of the thermoplastic polymer and the moisture-curable polyolefin. Not wishing to be limited by theory, crosslinking within the polymeric component can provide temperature resistance to the polymeric component, as well as to the composition comprising the polymeric component. Temperature resistance is quantified by measurement of the hot creep and hot deformation properties of the composition.

[0089] The extent of crosslinking within the polymeric component is correlated to the gel content of the composition, i.e., the extent of crosslinking is proportional to gel content. Alternatively, the extent of crosslinking within the polymeric component can be correlated to the hot creep value of the composition, the hot deformation value of the composition or a combination thereof. In an embodiment, the polymeric component is crosslinked as indicated by a gel content from 60%, or 65% to 70%, or 75%, or 80% as disclosed herein. In a further embodiment, the polymeric component is crosslinked as indicated by a hot creep value from 10%, or 20% to 30%, or 45% as disclosed herein. In a still further embodiment, the polymeric component is crosslinked as indicated by a hot deformation value from 7% to 36%, as disclosed herein.

[0090] In an embodiment, the polymeric component is crosslinked when the thermoplastic polymer is present in an amount from 5 to 40 wt %, the moisture-curable polyolefin is present in an amount from 55 to 90 wt %, and the moisture condensation catalyst is present in an amount from 3 to 7 wt %, wherein weight percentages are based on the total weight of the composition.

[0091] In an embodiment, the composition of the present disclosure is a non-foamed composition.

[0092] In an embodiment, the composition of the present disclosure is a thermoset composition.

[0093] In an embodiment, the composition of the present disclosure is void of monomer units derived from propylene.

[0094] In an embodiment, the composition has a surface smoothness from 3, or 13, or 25, or 51, or 89, or 102, or 114, to 127, or 140, or 149, or 152, or 162, or 178, or 184, or 191, or 203, or 216, or 229, or 254 μ.Math.in. In a further embodiment, the composition has a surface smoothness from 3 to 254 μ.Math.cm (1 to 100 μ.Math.in), or from 51 to 229 μ.Math.cm (20 to 90 μ.Math.in), or from 89 to 216 μ.Math.cm (35 to 85 μ.Math.in), or from 89 to 191 μ.Math.cm (35 to 75 μ.Math.in), or from 102 to 184 μ.Math.cm (40 to 72 μ.Math.in), or from to 102 to 162 μ.Math.cm (40 to 64 μ.Math.in), or from 102 to 127 μ.Math.cm (40 to 50 μ.Math.in).

[0095] In an embodiment, the composition has a hot creep value from 1%, or 5%, or 10%, or 15%, or 20% to 25%, or 30%, or 35%, or 40%, or 45%. In a further embodiment, the composition has a hot creep value from 1% to 45%, or from 5% to 43%, or from 10% to 41%, or from 10% to 35%, or from 10% to 30%, or from 10% to 25%.

[0096] In an embodiment, the composition has a hot deformation value from 1%, or 5%, or 7%, or 10%, or 15%, or 20% to 25%, or 30%, or 36%. In a further embodiment, the composition has a hot deformation creep value from 1% to 55%, or from 5% to 40%, or from 7% to 36%, or from 10% to 25%.

[0097] In an embodiment, the composition has a gel content from 60%, or 65% to 70%, or 75%, or 80%. In a further embodiment, the composition has a gel content from 60% to 80%, or from 65% to 75%.

Compounding and Fabrication

[0098] Melt blending of the thermoplastic polymer, moisture-curable polyolefin, moisture condensation catalyst, and optional filler and additives are performed by standard methods known to those skilled in the art. Examples of compounding equipment include BRABENDER™, BANBURY™ and BOLLING™ internal batch mixers. Continuous single or twin screw mixer or extruders suitable for use include DAVIS STANDARD™ extruders, FARREL™ continuous mixes, WERNER AND PFLEIDERER™ twin screw mixers, and BUSS™ 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.

[0099] The components of the composition are typically mixed at a temperature and for a length of time sufficient to fully homogenize the mixture but insufficient to cause the material to gel. The moisture condensation catalyst can be added to the moisture-curable polyolefin directly; or alternatively, added before, with or after the optional filler and additives are added to the moisture-curable polyolefin. Typically, the components are mixed together in a melt-mixing device. The mixture is then shaped into the final article. The temperature of compounding and article fabrication should be above the melting point of the moisture-curable polyolefin but preferably below 250° C.

[0100] In an embodiment, the moisture-curable polyolefin, the moisture condensation catalyst, the filler, the additive and combinations thereof are added in the form of a masterbatch.

[0101] In one embodiment, one or more of the components are dried before compounding, or a mixture of components is dried after compounding, to reduce or eliminate potential scorch that may be caused from moisture present in or associated with the component, e.g., filler.

[0102] In an embodiment, the polymeric composition is non-foamed and includes:

[0103] (A) from 5 wt % to 40 wt % HDPE;

[0104] (B) from 55 wt % to 90 wt % of an ethylene and vinyltrimethoxysilane copolymer; and

[0105] (C) from 0.05 wt % to 7 wt % of a dibutyl tin dilaurate moisture condensation catalyst; [0106] The polymeric composition having one, some, or all of the following properties: [0107] (i) a gel content from 60% to 80%; and/or [0108] (ii) a hot creep value from 10% to 45%; and/or [0109] (ii) a hot deformation value from 7% to 36% (hereafter referred to as polymeric composition 1).

Articles of Manufacture

[0110] In one embodiment, the composition of the present disclosure is applied to a conductor as a coating in known amounts and by known methods (for example, with the equipment and methods described in U.S. Pat. Nos. 5,246,783 and 4,144,202). Typically, the composition is prepared in a reactor-extruder equipped with a conductor-coating die and after the components of the composition are formulated, the composition is extruded over the conductor as the conductor is drawn through the die. The composition can be extruded over the conductor at a line speed from 800 to 2000 feet per minute (from 243 to 610 meters per minute, m/min). The cure phase of the process, during which crosslinks are created, may begin in the reactor-extruder. The shaped article can be exposed to either or both elevated temperature and external moisture and if an elevated temperature, it is typically between ambient and up to but below the melting point of the composition for a period of time such that the article reaches a desired degree of crosslinking. The temperature of any post-shaping cure should be above 0° C.

[0111] In an embodiment, the coating is an insulation layer in direct contact with the conductor. The term “in direct contact,” as used herein indicates that the conductor and the insulation layer are in an adhering relationship to one another such that the conductor is located immediately adjacent to the insulation layer and no intervening structure is present between the two.

[0112] In a particular embodiment, the insulation layer is used for twisted-pair category data cables. The insulation layer is suitable for all category data cable ratings including Cat2, Cat3, Cat4, Cat5, Cat5e, Cat6, Cat6a and Cat7. The category data cable can carry low voltage power that serves as a power source for electronic devices. Combined power and data cable applications are termed “Power over Ethernet” or “PoE.”

[0113] In an embodiment, the insulation layer has a thickness from 127 μm (5 Mil), or 178 μm (7 Mil), or 229 μm (9 Mil), or 254 μm (10 Mil), or 305 μm (12 Mil) to 381 μm (15 Mil), or 451 μm (18 Mil), or 508 μm (205 Mil). In a further embodiment, the insulation layer has a thickness from 127 μm (5 Mil) to 508 μm (205 Mil), or from 178 μm (7 Mil) to 381 μm (15 Mil), or from 229 μm (9 Mil) to 305 μm (12 Mil).

[0114] In an embodiment, the insulation layer is a non-foamed insulation layer.

[0115] In an embodiment, a coated conductor is provided and includes a conductor, and a coating on the conductor. The coating is a non-foamed polymeric composition composed of polymeric composition 1: [0116] (A) from 5 wt % to 40 wt % HDPE; [0117] (B) from 55 wt % to 90 wt % of an ethylene and vinyltrimethoxysilane copolymer; and [0118] (C) from 0.5 wt % to 7 wt % of a dibutyl tin dilaurate moisture condensation catalyst; [0119] the coating having one, some, or all of the following properties: [0120] (i) a surface smoothness from 102 μ.Math.cm to 184 μ.Math.cm; and/or [0121] (ii) a tensile strength from 1905 psig to 2410 psig; and/or [0122] (iii) a elongation from 215% to 265%.

[0123] Other articles of manufacture that can be prepared from the composition of the present disclosure include fibers, ribbons, sheets, tapes, tubes, pipes, weather-stripping, seals, gaskets, hoses, footwear and bellows. These articles can be manufactured using known equipment and techniques.

[0124] The present disclosure is described more fully through the following examples. Unless otherwise noted, all parts and percentages are by weight.

EXAMPLES

[0125] The raw materials for use in the Inventive Examples (“IE”) and Comparative Samples (“CS”) are detailed in Table 1 below.

TABLE-US-00001 TABLE 1 Commercial Name Composition & Properties Source AXELERON ™ High density polyethylene (HDPE) The Dow CS L-3364 NT Density: 0.945 g/cm.sup.3 Chemical Melt Index: 0.7 g/10 min Company AXELERON ™ High density polyethylene (HDPE) The Dow 6944 NT Density: 0.965 g/cm.sup.3 Chemical Melt Index: 8 g/10 min Company SI-LINK ™ Ethylene/vinyl trimethoxy silane The Dow DFDB-5451 NT copolymer with scorch retardant Chemical Density: 0.922 g/cm.sup.3 Company Melt index: 1.5 g/10 min @ 190° C./2.16 kg SI-LINK ™ LDPE masterbatch containing The Dow DFDA-5481 NT dibutyl tin dilaurate Chemical Density: 0.93 g/cm.sup.3 Company Melt index: 0.925 g/10 min @ 190° C./2.16 kg SI-LINK ™ LDPE masterbatch containing The Dow DFDA-5488 NT sulfonic acid Chemical Density: 1.45 g/cm.sup.3 Company Melt index: 0.925 g/10 min @ 190° C./2.16 kg

[0126] Polymeric compositions for Inventive Examples IE-1, IE-2, IE-3, IE-4, IE-5 and Comparative Samples CS-1 & CS-2 are prepared for coated conductor samples according to the formulations listed in Table 2 with the raw materials listed in Table 1.

[0127] Coated conductor samples are prepared from tinned, 7 strand, 24 American Wire Gauge (AWG) core. A composition of the components is first dry blended. The composition is then melt blended by extrusion blending with a 2.5 inch DAVIS STANDARD extruder having 22:1 LID and fitted with a PE screw having a dual flight mixing section. The melt blended composition is extruded over the conductor as the conductor is drawn through the extruder die at a line speed of 548 meters per minute. The temperature profile of the extruder is 150° C. to 182° C. across four zones. The extruded coated conductor is cured in a 90° C. water bath for 14-18 hours and then dried in a convection oven overnight at 80° C., or cured in a humidity chamber at 50° C. and 75% relative humidity for 14 days and then dried overnight at 80° C.

[0128] The thickness of the coated conductor is 254 μm (10 Mil).

[0129] Polymeric compositions for Inventive Examples IE-7, IE-8, IE-9, IE-10, IE-11 and Comparative Samples CS-3, CS-4, CS-5 & CS-6 are prepared for tape samples according to the formulations listed in Table 2 with the raw materials listed in Table 1.

[0130] Tape samples are prepared by first dry blending a composition of the components. The composition is then melt blended by extrusion blending into 2 inch tape with a ¾ inch single screw BRABENDER™ batch mixer having 25:1 LID and fitted with a Maddox mixing screw. The melt blended composition is extruded at 50 revolutions per minute (rpm) and a take-up speed of 38 feet per minute. The temperature profile of the extruder is from 150° C. to 182° C. across all five zones. The extruded tape is cured in a 90° C. water bath for 14-18 hours and then dried in a convection oven overnight at 80° C., or cured in a humidity chamber at 50° C. and 75% relative humidity for 14 days and then dried overnight at 80° C.

[0131] The test results formulations for the Inventive Examples and Comparative Samples are reported in Table 2 below.

TABLE-US-00002 TABLE 2 Coated Conductor Weight Percentage Tape Sample Weight Percentage CS-1 CS-2 IE-1 IE-2 IE-3 IE-4 IE-5 CS-3 L-3364 100 5 10 15 20 40 DFDB-5451 95 90 85 80 75 55 DFDA-5481 5 5 5 5 5 5 6944 NT 100 DFDA-5488 Total 100 100 100 100 100 100 100 100 Surface NT* 229 184 162 149 127 102 Smoothness (μ-cm) Hot Creep broke/ 24.98 28.87 26.71 26.5 28.24 33.03 (%) fail Tensile NT* 1822.2 1905.2 2087.8 2175 2187.4 2405.2 Strength (psig) Elongation NT* 213.2 218 238.2 241.4 226.6 261.4 (%) Line speed 548 548 548 548 548 548 548 (m/min) Hot Creep Fail (%) Hot 100 Deformation at 150° C. (%) Gel Content 0.92 (%) Tape Sample Weight Percentage CS-4 CS-5 CS-6 IE-7 IE-8 IE-9 IE-10 IE-11 L-3364 100 5 10 20 40 20 DFDB-5451 95 95 90 85 75 55 75 DFDA-5481 5 5 5 5 5 6944 NT DFDA-5488 5 5 Total 100 100 100 100 100 100 100 100 Surface Smoothness (μ-cm) Hot Creep (%) Tensile Strength (psig) Elongation (%) Line speed (m/min) Hot Creep Fail 9.9 15.3 11.1 10.5 15.9 40.4 27.3 (%) Hot 100 7.3 −0.1 6.6 11.2 10.6 35.7 9.2 Deformation at 150° C. (%) Gel Content 1.47 51.16 82.28 79.45 74.46 65.41 59.12 64.92 (%) *NT: Not tested

Results and Discussion

[0132] CS-1 and CS-2 are coated conductors. CS-1 is wire coated with HDPE having no crosslinking that fails the hot creep test. CS-2 is wire coated with a crosslinked polymer containing no thermoplastic component. CS-2 has the least favorable results for surface smoothness and tensile properties of all the coated conductors investigated.

[0133] CS-3 through CS-6 are tape samples. CS-3 and CS-4 are HDPE thermoplastic compounds with no crosslinking. CS-3 and CS-4 each exhibit poor tensile properties: hot creep value of 100% and failure of the hot deformation test. The CS-5 tape sample has no thermoplastic component and exhibits the lowest extent of crosslinking, (gel content of 51%), of all tape samples investigated. CS-6 is an acid-catalyzed crosslinked composition containing no thermoplastic compound. The CS-6 tape sample swells during the hot deformation test as indicated by the negative result posted. CS-6 has extensive crosslinking as indicated by a gel content of 82%.

[0134] Applicant discovered non-foamed, insulative compositions of a thermoplastic polymer and a moisture-curable polyolefin that are crosslinked as indicated by a gel content percentage from 60 to 82.

[0135] The inventive compositions (IE-1 to IE-5), unexpectedly provide insulated coated conductor articles having: (i) surface smoothness from 102 to 184 μ.Math.cm (40 to 72 μ.Math.in) that is from 44% to 80% improved over crosslinked compositions containing no thermoplastic polymer; (ii) hot creep percentage from 26.5 to 33.0 that is from 8% to 30% improved over crosslinked compositions containing no thermoplastic polymer; and (iii) tensile strength from 1905 to 2410 prig that is from 5% to 132% improved over crosslinked compositions containing no thermoplastic polymer.

[0136] The inventive compositions (IE-7 to IE-11), unexpectedly provide tape articles having: (i) hot creep percentage from 11.1 to 40.4 that is from 12% to 308% improved over crosslinked compositions containing no thermoplastic polymer; and (ii) hot deformation percentage from 9.2 to 35.7 that is from 26% to 390% improved over crosslinked compositions containing no thermoplastic polymer.

[0137] It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come with the scope of the following claims.