US20210079176A1 - Masterbatch with semi-crystalline polyolefin carrier resin - Google Patents

Masterbatch with semi-crystalline polyolefin carrier resin Download PDF

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Publication number
US20210079176A1
US20210079176A1 US16/961,441 US201816961441A US2021079176A1 US 20210079176 A1 US20210079176 A1 US 20210079176A1 US 201816961441 A US201816961441 A US 201816961441A US 2021079176 A1 US2021079176 A1 US 2021079176A1
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Prior art keywords
coagent
masterbatch
semi
ebc
ethylene
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Inventor
Yong Yong Yang
Dachao Li
Yabin Sun
Timothy J. Person
Jeffrey M. Cogen
Pual J. Caronia
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Down Global Technologies LLC
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Down Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes

Definitions

  • Patent publications include CN103865420(A), DE102006017346A1, EP1433811A2, EP2889323A1, U.S. Pat Nos. 5,367,030, 6,187,847B1, 6,191,230B1, 6,936,655B2, US20020198335A1, US20080176981A1, U.S. Pat. Nos. 8,449,801B1, 8,691,984B2, 9,147,784B2.
  • composition of paragraph [0074] is made by direct compounding and once made is used directly to make a film.
  • the composition has 110.1 total weight parts and is made from 100 weight parts of an HDPE having melt index (I 2 ) 0.04 g/10 min., 2 weight parts (1.82 weight percent) of triallyl propyl isocyanuric acid ester, 6 weight parts of TiO2, 2 weight parts of vinyl tri(beta-methoxyethoxy)silane, and 0.1 weight part of 2-hydroxy-4-benzophenone.
  • EP2889323A1 to S. Deveci et al. for polymer composition comprising carbon black and a carrier polymer for the carbon black.
  • a masterbatch is a solid or liquid additive concentrate formulation used for conveying an additive into a host polymer in need thereof.
  • the host polymer sometimes called a host resin, base resin, or base polymer
  • the additive may be used to enhance the rate or extent of curing of the host polymer or enhance the performance of the cured product.
  • the typical masterbatch comprises the additive and a carrier resin, sometimes called a carrier polymer.
  • the formulation is made by mixing or blending a smaller amount of the masterbatch with a significantly larger amount of the host polymer.
  • the concentration of the additive in the masterbatch is significantly higher than its concentration in the formulation.
  • Electron-beam irradiation is useful in a method of curing (crosslinking) polyolefins.
  • the method comprises applying a dose of electron-beam irradiation to an (electron beam)-curable (EBC) polyolefin compound to give a cured polyolefin product.
  • EBC electron beam-curable
  • the method forms covalent bonds directly between polyolefin macromolecules of the EBC polyolefin compound.
  • the electron-beam curing method may be used to cure various types of polyolefins including low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE).
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • HDPE high density polyethylene
  • Crosslinked low density polyethylene XLDPE
  • crosslinked linear low density polyethylene XLLDPE
  • the crosslinked polyethylenes should have adequate hot creep (hot set) performance (i.e., retain its shape at operating temperature).
  • Hot creep performance of (electron beam)-crosslinked high density polyethylene is usually weaker than that of (electron beam)-crosslinked linear low density polyethylene.
  • Severity of the problems may be attenuated by mixing a minor amount of coagent additive into the EBC polyolefin compound to give an (electron beam)-curable (EBC) formulation comprising the EBC polyolefin compound and the coagent.
  • the EBC formulation can be cured at a lower dose of the electron-beam irradiation than the dose used to cure the EBC polyolefin compound without coagent.
  • the resulting cured polyolefin product can reach an equal or greater cure state than that of a comparative cured polyolefin product prepared without the coagent at the same lower EB dose. All other things being equal, the higher the loading of the coagent in the EBC formulation, the lower the dose of electron-beam irradiation that may be used to achieve a given cure state.
  • the EBC polyolefin compound used as a host polymer in coatings on wire and cable may be a polyethylene such as a low density polyethylene (LDPE) or a linear low density polyethylene (LLDPE).
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • the typical coagent for these coatings has a polar backbone or substructure to which two or more alkenyl groups are bonded, such as triallyl isocyanurate (TAIC). It can be problematic to store an EBC formulation of the LDPE and/or LLDPE (host polymer) and 0.5 wt% or higher coagent without sweat out of coagent at room temperature.
  • TAIC triallyl isocyanurate
  • the rate and/or extent of sweat out may worsen with increasing storage time and/or temperature (an elevated temperature above room temperature and below the melting temperature of the LDPE and/or LLDPE).
  • porous polymer pellets may be tried.
  • Porous polymer pellets are commercially available. For example, Membrana GmbH, Obernburg, Germany, supply ACCUREL XP and ACCUREL MP brands of porous polymer pellets. These porous polymer pellets are composed of polypropylene, HDPE, LDPE, LLDPE, EVA, EMA, PC, PMMA, PA6, PA12, PS, SBC, SAN, PET, or Bio Polyester, PLA. These porous pellets are said to have an additive loading capacity of up to 50% to 70% depending on the particular product and additive being loaded.
  • porous polymer pellets include limited polymer selection and leakage of additive from pores of loaded pellets. Problems are more acute when the additive is a liquid, especially one of low surface tension and low viscosity at room temperature (23 degrees Celsius (° C.)).
  • the squeezing/compressing can push the liquid additive out of the pores of the porous polymer pellets. Any resulting product that contains or is prepared from the loaded porous polymer pellets may have an insufficient quantity of the additive for its intended use.
  • the technical solution comprises a carrier resin that is a semi-crystalline polyolefin.
  • the semi-crystalline polyolefin may be substantially nonporous and useful for conveying the coagent into an EBC polyolefin compound (host polymer) such as a LDPE and/or LLDPE.
  • the semi-crystalline polyolefin is capable of carrying high loadings of the coagent, such as up to 20 wt %, and may be more, of TAIC, without sweat out thereof at room temperature during storage or leakage during handling comprising compressing or squeezing.
  • the inventive carrier resin may be capable of carrying high loadings of the liquid or solid coagent without seepage or leakage thereof.
  • the semi-crystalline polyolefin defines tortuous pathways therein that trap the coagent, releasing the coagent only after the crystalline portion of the semi-crystalline polyolefin has been melted. Without being bound by theory, we believe this advantage prevents the coagent from prematurely flowing out of heated semi-crystalline polyolefin, such as granules or pellets, before they can be fully mixed into a melt of an EBC polyolefin compound (host polymer).
  • the technical solution enables and includes an inventive coagent masterbatch that comprises a semi-crystalline polyolefin (carrier resin) containing an alkenyl-functional coagent.
  • inventive coagent masterbatch that comprises a semi-crystalline polyolefin (carrier resin) containing an alkenyl-functional coagent.
  • inventive coagent masterbatch that comprises a semi-crystalline polyolefin (carrier resin) containing an alkenyl-functional coagent.
  • an EBC formulation comprising the inventive masterbatch and an EBC polyolefin compound (host polymer); a cured polyolefin product prepared by electron-beam irradiating the EBC formulation; methods of making and using same masterbatch, formulation, and product; and articles containing or made from same masterbatch, formulation, and product.
  • the cured polyolefin product has both direct polyolefin-polyolefin bonds and polyolefins crosslinked via a multivalent crosslinking group
  • a formulator can use the inventive masterbatch to quickly make the EBC formulation and a manufacturer can use the EBC formulation to make cured polyolefin products with fewer defects relative to a comparative EBC polyolefin compound (host polymer) free of coagent and cured polyolefin product made therefrom.
  • the sweat out/leakage stability of the inventive coagent masterbatch enables the formulator and manufacturer to stockpile the coagent masterbatch. It also enables the manufacturer to use coagent masterbatch from the stockpile to make the EBC formulation just prior to electron-beam curing in order to shorten or eliminate the storage of the EBC formulation, thereby avoiding any risk of coagent sweat out from the EBC formulation.
  • a coagent masterbatch comprising (A) a semi-crystalline polyolefin carrier resin and (B) an alkylene-functional coagent disposed in the (A) semi-crystalline polyolefin carrier resin; wherein (A) is 80.0 to 99.9 weight percent (wt %), alternatively 80.0 to 99.0 wt %, alternatively 80.0 to 98.9 wt %, alternatively 84 to 98.9 wt %, alternatively 84 to 98.8 wt %, alternatively 85 to 94 wt %, and (B) is from 20.0 to 0.1 wt %, alternatively 20.0 to 1.0 wt %, alternatively 20.0 to 1.1 wt %, alternatively 16 to 1.1 wt %, alternatively 16 to 1.2 wt %, alternatively 15 to 6 wt %, respectively, of the combined weight of constituents (A) and (B); wherein the (A) semi-crystalline polyole
  • the (A) semi-crystalline polyolefin carrier resin is in a divided solid form such as powder, granules, pellets, or a combination of any two or more thereof.
  • the term “when” above refers to a non-limiting embodiment of the (A) semi-crystalline polyolefin carrier resin.
  • the coagent masterbatch includes additional embodiments when the (A) semi-crystalline polyolefin carrier resin is not the semi-crystalline polyethylene.
  • the coagent masterbatch of aspect 1 characterized by any one of limitations (i) to (x): (i) the coagent masterbatch is free of (C) an (electron beam)-curable polyolefin compound (host polymer) other than constituent (A); (ii) the coagent masterbatch further comprises at least one additive independently selected from optional additives (D) to (L): (D) a flame retardant, (E) an antioxidant, (F) a processing aid, (G) a colorant, (H) a metal deactivator, (I) an (unsaturated carbon-carbon bond)-free hydrolyzable silane, (J) a corrosion inhibitor, (K) a hindered amine light stabilizer, and (L) an ethylene-based copolymer that is different than constituents (A) and (C) and is an ethylene/(C 4 -C 20 )alpha-olefin copolymer, an ethylene/unsaturated carboxylic ester cop
  • Aspect 3 The coagent masterbatch of aspect 1 or 2 wherein the (A) semi-crystalline polyolefin carrier resin comprises, alternatively consists essentially of, alternatively consists of any one of (i) to (viii): (i) a semi-crystalline medium density polyethylene; (ii) a semi-crystalline high density polyethylene; (iii) a semi-crystalline polypropylene; (iv) a semi-crystalline ethylene/propylene copolymer; (v) a semi-crystalline poly(ethylene-co-alpha-olefin) copolymer; (vi) a combination (e.g., mixture or blend) of any two or more of (i), (ii) and (v); (vii) the (A) semi-crystalline polyolefin carrier resin has a crystallinity of 57.5 to ⁇ 100 wt %, alternatively 60.0 to ⁇ 100 wt %, alternatively 65 to ⁇ 100 wt %, alternatively 70.0 to ⁇ 100 w
  • Aspect 4 The coagent masterbatch of any one of aspects 1 to 3 wherein the (A) semi-crystalline polyolefin carrier resin has any one of (i) to (viii): (i) a density of greater than 0.936 (g/cm 3 , alternatively at least 0.940 g/cm 3 , and is a polyethylene; (ii) a density of 0.89 to 0.946 g/cm 3 , alternatively 0.900 to 0.940 g/cm 3 , and is a polypropylene; (iii) a crystallinity of 60.0 to ⁇ 100 wt %, alternatively 65 to ⁇ 100 wt %, alternatively 70.0 to ⁇ 100 wt %, alternatively 75 to ⁇ 100 wt % (Crystallinity Test Method using DSC) and is a polyethylene; (iv) a melt index (I 2 , 190° C./2.16 kg load) of 0.1 to 20 grams per 10 minutes (g/10
  • Aspect 5 The coagent masterbatch of any one of aspects 1 to 4 wherein the (B) alkenyl-functional coagent is as described by any one of limitations (i) to (viii):
  • (i) (B) is 2-allylphenyl allyl ether; 4-isopropenyl-2,6-dimethylphenyl allyl ether; 2,6-dimethyl-4-allylphenyl allyl ether; 2-methoxy-4-allylphenyl allyl ether; 2,2′-diallyl bisphenol A; 0,0′-diallyl bisphenol A; or tetramethyl diallylbisphenol A;
  • (ii) (B) is 2,4-diphenyl-4-methyl-1-pentene or 1,3-diisopropenylbenzene;
  • (iii) (B) is Many!
  • (B) is trimethylolpropane triacrylate, trimethylolpropane trimethylacrylate, ethoxylated bisphenol A dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, or propoxylated glyceryl triacrylate; (v) (B) is a polybutadiene having at least 50 wt % 1,2-vinyl content or trivinyl cyclohexane; (vi) (B) is an alkenyl-functional organosiloxane of formula (I): [R 1 ,R 2 SiO 2/2 ] n
  • a method of storing a coagent masterbatch comprising maintaining for at least 20 days the coagent masterbatch of any one of aspects 1 to 5 at a temperature from 20° to 25° C. to give a stored coagent masterbatch without sweat out of the alkenyl-functional coagent as measured by Sweat Out Test Method (Quantitative, described later).
  • Aspect 7 An (electron beam)-curable formulation comprising the coagent masterbatch of any one of aspects 1 to 5, or the stored coagent masterbatch made by the method of aspect 6, and (C) an electron-beam curable (EBC) polyolefin compound.
  • EBC electron-beam curable
  • Aspect 8 The (electron beam)-curable formulation of aspect 7 characterized by any one of limitations (i) to (xiii): (i) the (C) EBC polyolefin compound is a low density polyethylene (LDPE) having a density from 0.910 to 0.925 g/cm 3 ; (ii) the (C) EBC polyolefin compound is a linear low density polyethylene (LLDPE) having a density from 0.910 to 0.925 g/cm 3 ; (iii) the (C) EBC polyolefin compound is a medium density polyethylene (MDPE) having a density from 0.926 to 0.940 g/cm 3 ; (iv) the (C) EBC polyolefin compound is a high density polyethylene (HDPE) having a density from 0.941 to 0.990 g/cm 3 ; (v) the (C) EBC polyolefin compound is a polyethylene elastomer selected from elastomers
  • a method of making an (electron beam)-curable formulation comprising mixing together a divided solid form of the coagent masterbatch of any one of aspects 1 to 5, or the stored coagent masterbatch made by the method of aspect 6, and a (C) EBC polyolefin compound in divided solid or melt form so as to give a mixture; and melt mixing or extruding the mixture so as to make the (electron beam)-curable (EBC) formulation.
  • the EBC formulation that is made is the EBC formulation of aspect 8.
  • the extruded EBC formulation may be pelletized to give the EBC formulation as solid pellets.
  • the extruded EBC formulation may be cooled to give the EBC formulation as a shaped solid such as an insulation layer on a cable.
  • a method of electron-beam curing a formulation in need thereof comprising irradiating the EBC formulation of aspect 7 or 8, or the (electron beam)-curable formulation made by the method of aspect 9, with an effective dose of electron-beam irradiation so as to give an electron-beam cured polyolefin product.
  • coagent masterbatch is the stored coagent masterbatch made by the method of aspect 6.
  • the method further comprises a preliminary step before the irradiating step of maintaining for from 1 to 100 days, alternatively from 5 to 50 days, alternatively from 14 to 20 days the coagent masterbatch of any one of aspects 1 to 5 at a temperature from 20° to 25° C.
  • the EBC formulation in a shaped solid form may be cured by the method to give a shaped form of the electron-beam-cured polyolefin product.
  • the product may have a defined shape such as a coating, film, or molded or extruded shape.
  • a manufactured article comprising the electron-beam-cured polyolefin product of aspect 11 and a component in operative contact therewith.
  • a coated conductor comprising a conductive core and a polymeric layer at least partially surrounding the conductive core, wherein at least a portion of the polymeric layer comprises the electron-beam-cured polyolefin product of aspect 11.
  • a method of conducting electricity comprising applying a voltage across the conductive core of the coated conductor of aspect 13 so as to generate a flow of electricity through the conductive core.
  • Additive a solid or liquid compound or substance that imparts a desired property to a host polymer, or to a formulation comprising a masterbatch and host polymer, or to a reaction product prepared therefrom.
  • the property may be a chemical, electrical, mechanical, optical, physical, and/or thermal property.
  • Carrier resin a divided solid (particulate) polymer used for temporarily holding and later releasing an additive.
  • Coagent a multifunctional compound that enhances crosslinking of (co)polymer macromolecules during a curing method.
  • a single coagent molecule may react with two, three, or more (co)polymer macromolecules to make crosslinked (co)polymer macromolecular products wherein two, three, or more of the (co)polymer macromolecules have been covalently bonded to a same multivalent crosslinking group derived from the coagent molecule.
  • Coagent is also known as a curing coagent or crosslinking cogent.
  • Typical coagents are acyclic or cyclic compounds that contain carbon atoms or silicon atoms in their respective backbone or ring substructure.
  • the backbone or ring substructure of a coagent is based on carbon (carbon-based substructure) or silicon (silicon-based substructure).
  • Coagent is different in structure and function than a cure agent.
  • Coagent masterbatch A masterbatch wherein the additive comprises a coagent.
  • the coagent masterbatch may contain at least 45 wt %, alternatively at least 50 wt %, alternatively at least 55 wt %, alternatively at least 70 wt %, alternatively at least 80 wt %, alternatively at least 90 wt % of the (A) semi-crystalline polyolefin carrier resin; all based on total weight of the coagent masterbatch.
  • the coagent masterbatch may contain from 55 to 1 wt %, alternatively 50 to 1 wt %, alternatively 45 to 1 wt %, alternatively 30 to 1 wt %, alternatively 20 to 1 wt %, alternatively 10 to 1 wt % of the (B) alkenyl-functional coagent.
  • the coagent masterbatch may be free of: (i) an ethylene/silane copolymer, (ii) an ethylene/vinyl acetate (EVA) copolymer, (iii) an ethylene/alkyl acrylate copolymer (e.g., EEA copolymer), (iv) carbon black; (v) a pigment or colorant; (vi) a filler; (vii) any two, alternatively any six of (i) to (vi).
  • EVA ethylene/vinyl acetate
  • EEA copolymer ethylene/alkyl acrylate copolymer
  • the coagent masterbatch may have from >0 to 5 wt % of any other carrier resin such as a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), an ethylene/alpha-olefin copolymer, an EEA copolymer, a polypropylene, a nylon (e.g., Nylon 6 or 66), a BPA-PC, a polycarbonate, a BPA-PS, a polysulfone, or a polyphenylene oxide; alternatively the coagent masterbatch may be free of any carrier resin, or any resin, other than the (A) semi-crystalline polyolefin carrier resin.
  • the coagent masterbatch may further comprise a filler.
  • the filler may be calcium carbonate, zinc borate, zinc molybdate, zinc sulfide, carbon black, talc, magnesium oxide, zinc oxide, or a clay.
  • the coagent masterbatch may be free of any additive that prevents electron-beam curing of the host polymer.
  • Coated conductor a material for conducting electricity at least partially covered by a layer of a protective material.
  • An example is an electrical power cable.
  • Comonomer composition distribution or chemical composition distribution is the variability of the amounts of comonomeric units incorporated into copolymer macromolecules.
  • CCD Comonomer composition distribution
  • the CCD is said to be “broad”.
  • the amount of comonomeric units incorporated into the copolymer macromolecules is relatively consistent from copolymer macromolecule to copolymer macromolecule, the CCD is said to be “narrow”.
  • a measurement of CCD is comonomer distribution breadth index (CDBI).
  • Comonomer distribution breadth index is the weight percent (wt %) of copolymer molecules having a comonomeric unit content within 50 percent (i.e., ⁇ 50%) of the median total molar comonomeric unit content. Such a relatively high CDBI value indicates that the copolymer molecules are relatively uniform in comonomeric unit content.
  • the CDBI value of a linear polyethylene homopolymer, which does not contain a comonomer, is defined to be 100%.
  • the higher CDBI value indicates that the comonomer distribution of the first copolymer is more controlled or limited than the comonomer distribution of the second copolymer.
  • (Co)polymer polymer (homopolymer) and/or copolymer.
  • a homopolymer is a macromolecule composed of monomeric units derived from only one monomer and no comonomer units.
  • a copolymer is a macromolecule or collection of macromolecules having monomeric units and one or more different types of comonomeric units, wherein the monomeric units comprise on average per molecule a majority of the total units.
  • the copolymer's monomeric units are made by polymerizing a first monomer and the one or more different types of comonomeric units are made by polymerizing one or more different second or more monomers, referred to as comonomers.
  • Monomers and comonomers are polymerizable molecules.
  • a monomeric unit also called a monomer unit or “mer” is the largest constitutional unit contributed by (derived from) a single monomer molecule to the structure of the macromolecule(s).
  • a comonomeric unit also called a comonomer unit or “comer” is the largest constitutional unit contributed by (derived from) a single comonomer molecule to the structure of the macromolecule(s). Each unit is typically divalent (prior to any curing or crosslinking).
  • a “bipolymer” is a copolymer made from a monomer (e.g., ethylene) and one type of comonomer (e.g., 1-hexene).
  • a “terpolymer” is a copolymer made from a monomer (e.g., ethylene) and two different types of comonomers (e.g., propylene and 1,3-butadiene).
  • comonomers e.g., ethylene, butadiene
  • Cure agent a radical-generating compound (in situ) that upon activation forms a free-radical and initiates or enhances reactions involving crosslinking of macromolecules. Activation of the cure agent may be achieved by subjecting the cure agent to heat or light.
  • cure agents are peroxides, diazo-functional organic compounds, and 2,3-dimethyl-2,3-diphenylbutane.
  • peroxides are hydrogen-organic peroxides of formula H—O—O—R and organic peroxides of formula R—O—O—R, wherein each R is independently a hydrocarbyl group.
  • Curing crosslinking to form a crosslinked product (network polymer).
  • Divided solid a particulate material in a state of matter characterized by relatively stable shape and volume. Examples are powers, granules, and pellets.
  • Effective dose a quantity sufficient to result in crosslinking of a polyolefin in need thereof and receiving the quantity.
  • Electron-beam curable capable of being cured by irradiation (treatment) with high-energy beta radiation such as from a high-energy electron-beam accelerator.
  • high-energy beta radiation such as from a high-energy electron-beam accelerator.
  • the irradiation induces covalent bonding (crosslinking) between adjacent macromolecules to form a network polymer.
  • High density polyethylene having a density from 0.941 to 0.990 g/cm 3 , an alpha-olefin comonomeric unit content greater than 0 wt %, and short chain branching.
  • Linear low density polyethylene having density from 0.910 to 0.925 g/cm 3 , an alpha-olefin comonomeric unit content greater than 0 wt %, and short chain branching.
  • the LLDPE may have a comonomer distribution breadth index (CDBI) of from 70 to less than 100 weight percent.
  • LDPE Low density polyethylene
  • MDPE Medium density polyethylene
  • Manufactured article man-made (by hand or machine) thing.
  • Melt a liquid formed by heating a solid material above its highest melting temperature.
  • Polyolefin a macromolecule, or collection of macromolecules, composed of constitutional units derived from polymerizable olefins.
  • Semi-crystalline a solid material having a first region that is neither crystalline nor amorphous and a second region that is amorphous. Having a percent crystallinity, typically between 10% and 90%, as measured by the Crystallinity Test Method described later.
  • Shaped solid a state of matter of relatively constant volume and external form, which is man-made (by hand or machine). E.g., extruding, molding, or coating a fluid into the external form, followed by cooling the external form in place to give a shaped solid.
  • Sweat out slow release of a liquid from a solid material containing the liquid therein.
  • the coagent masterbatch, EBC formulation, and cured polyolefin product may be referred to herein as the inventive masterbatch, formulation, and product, respectively.
  • the inventive masterbatch, formulation, and/or product may be free of an additive that is an acid condensation catalyst.
  • the acid condensation catalyst are (i) an organosulfonic acid, an organophosphonic acid, or a hydrogen halide; (ii) an organosulfonic acid; (iii) an alkyl-substituted arylsulfonic acid; (iv) an alkyl-substituted arylsulfonic acid wherein there is/are 1 or 2 (C 5 -C 20 )alkyl substituent(s) and 1 aryl group that is phenyl or naphthyl; (v) a (C 1 -C 5 )alkylphosphonic acid, wherein the (C 1 -C 5 )alkyl is unsubstituted or substituted with one —NH 2 group; (vi) HF, HCl, or HBr; (vii) a Lewis acid; or (viii) a combination of any two or more of
  • the inventive masterbatch, formulation, and/or product may be free of TiO 2 .
  • the inventive masterbatch and/or formulation may have greater than or equal to 2.0 weight percent of coagent, may have a MI greater than or equal to 0.1 g/10 minutes, or a combination of any two or more thereof.
  • the inventive masterbatch, formulation, and/or product may be free of a cure agent such as a peroxide such as a hydrogen-organic peroxide or an organic peroxide.
  • Coagent masterbatch is a divided solid such as a powder, granules and/or pellets.
  • Electron-beam curable formulation The total weight of all constituents and additives in the inventive masterbatch, formulation, and product independently is 100.00 wt %.
  • the electron-beam curable formulation may be a one-part formulation, alternatively a two-part formulation.
  • the two-part formulation may comprise first and second parts, wherein the first part consists essentially of the coagent masterbatch and the second part consists essentially of the (C) EBC polyolefin compound.
  • the semi-crystalline polyolefin carrier resin may be a semi-crystalline polyethylene that is a semi-crystalline medium density polyethylene (MDPE), a semi-crystalline high density polyethylene (HDPE), or a combination thereof.
  • Constituent (A) semi-crystalline polyolefin carrier resin may be in any divided solid form such as powder, granules, pellets, or a combination of any two or more thereof.
  • the semi-crystalline HDPE may have a maximum density of 0.970 g/cm 3 , alternatively at most 0.960 g/cm 3 , alternatively at most 0.950 g/cm 3 .
  • the semi-crystalline HDPE may have a density of from >0.935 to 0.970 g/cm 3 , alternatively 0.935 to 0.965 g/cm 3 .
  • the density of the (A) may be measured by ASTM D-1505, Test Method for Density of Plastics by the Density - Gradient Technique.
  • the (A) semi-crystalline polyolefin carrier resin may have a crystallinity of at least 55 wt %, alternatively at least 58 wt %, alternatively at least 59 wt %. In any one of the immediately preceding aspects the crystallinity may be at most 90 wt %, alternatively at most 80 wt %, alternatively at most 78 wt %.
  • the crystallinity is from 55 to 80 wt %, alternatively from 58 to 78 wt %, alternatively from 58 to 76 wt %, alternatively from 62 to 78 wt %, alternatively any one of 59 ⁇ 1 wt %, 62 ⁇ 1 wt %, 76 ⁇ 1 wt %, and 77 ⁇ 1 wt %.
  • the crystallinity of a semi-crystalline polyolefin resin such as (A) semi-crystalline polyolefin carrier resin, may be determined by differential scanning calorimetry (DSC) according to ASTM D3418-15 or the Crystallinity Test Method using DSC described later.
  • wt % crystallinity ( ⁇ H f *100%)/292 J/g.
  • wt % crystallinity ( ⁇ H f *100%)/165 J/g.
  • ⁇ H f is the second heating curve heat of fusion for the polyethylene resin or polypropylene resin, as the case may be, * indicates mathematical multiplication, / indicates mathematical division, 292 J/g is a literature value of the heat of fusion ( ⁇ H f ) for a 100% crystalline polyethylene, and 165 J/g is a literature value of the heat of fusion ( ⁇ H f ) for a 100% crystalline polypropylene.
  • crystallinity is determined by DSC according to the Crystallinity Test Method described later.
  • the (A) semi-crystalline polyolefin carrier resin may have a melt index (I 2 , 190° C./2.16 kg load) of 10 to 20 g/10 min., alternatively 0.1 to 10 g/10 min., alternatively 0.20 to 9 g/10 min.
  • the I 2 may be determined by ASTM D1238 as described later.
  • the (A) semi-crystalline polyolefin carrier resin may be characterized by a molecular weight distribution (MWD) that is monomodal, alternatively bimodal.
  • MFD molecular weight distribution
  • the (A) semi-crystalline polyolefin carrier resin may be a semi-crystalline HDPE that is bimodal and has a density of from 0.950 to 0.958 g/cm 3 and a melt index of from 0.20 to 0.40 g/10 min.
  • the (A) semi-crystalline polyolefin carrier resin may be a semi-crystalline HDPE that is monomodal and has a density of from 0.930 to 0.970 g/cm 3 and a melt index of from 0.65 to 9 g/10 min., alternatively a density from 0.935 to 0.965 g/cm 3 and a melt index from 0.7 to 8.5 g/10 min.
  • Constituent (B) alkenyl-functional coagent A molecule that contains a backbone or ring substructure and two or more propenyl, acrylate, and/or vinyl groups bonded thereto, or a collection of such molecules.
  • the backbone or substructure is composed of carbon atoms and optionally nitrogen atoms and is free of silicon atoms.
  • the backbone or substructure is composed of silicon atoms and optionally oxygen atoms.
  • the (B) may be a propenyl-functional coagent as described by any one of limitations (i) to (v), a vinyl-functional coagent as described by any one of limitations (vi) to (vii), or a combination thereof as described in limitation (viii):
  • (i) (B) is 2-allylphenyl allyl ether; 4-isopropenyl-2,6-dimethylphenyl allyl ether; 2,6-dimethyl-4-allylphenyl allyl ether; 2-methoxy-4-allylphenyl allyl ether; 2,2′-diallyl bisphenol A; O,O′-diallyl bisphenol A; or tetramethyl diallylbisphenol A;
  • (ii) (B) is 2,4-diphenyl-4-methyl-1-pentene or 1,3-diiso
  • (B) is a mixture of any two of the propenyl-functional coagents in (i).
  • the (B) may be an acrylate- functional conventional coagent selected from trimethylolpropane triacrylate (“TMPTA”), trimethylolpropane trimethylacrylate (“TMPTMA”), ethoxylated bisphenol A dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, and propoxylated glyceryl triacrylate; (vi) polybutadiene having at least 50 wt % 1,2-vinyl content; (vii) trivinyl cyclohexane (“TVCH”) (viii) a combination or any two or more of the foregoing coagents.
  • TMPTA trimethylolpropane triacrylate
  • TMPTMA trimethylolpropane trimethylacrylate
  • the (B) may be a coagent described in U.S. Pat. No. 5,346,961 or U.S. Pat. No. 4,018,852.
  • the (B) is the propenyl-functional coagent as described by any one of limitations (i) to (v).
  • the (B) is the propenyl-functional coagent selected from TAIC, TAC, TATM, HATATA, TMPTA, and TMPTMA; alternatively TAIC, TAC, and TMPTMA; alternatively TAIC; alternatively TAC; alternatively TATM; alternatively HATATA; alternatively TMPTA; alternatively TMPTMA.
  • the (B) is the monocyclic organosiloxane of formula (I). In some aspects the (B) is the monocyclic organosiloxane of formula (I), wherein subscript n is an integer 3 or 4; each R 1 is independently a (C 2 -C 4 )alkenyl; and each R 2 is (C 1 -C 4 )alkyl. In some aspects the (B) is the monocyclic organosiloxane of formula (I), wherein subscript n is an integer 3 or 4; each R 1 is independently a (C 2 -C 4 )alkenyl; and each R 2 is (C 1 -C 4 )alkyl.
  • the (B) is the monocyclic organosiloxane of formula (I), wherein subscript n is an integer 3 or 4; each R 1 is independently a (C 2 )alkenyl (i.e., vinyl); and each R 2 is methyl.
  • the (B) is the propenyl-functional coagent or the monocyclic organosiloxane of formula (I).
  • the propenyl-functional coagent is selected from TAIC, TAC, TATM, HATATA, TMPTA, and TMPTMA; alternatively TAIC, TAC, and TMPTMA; alternatively TAIC; alternatively TAC; alternatively TATM; alternatively HATATA; alternatively TMPTA; alternatively TMPTMA; and the monocyclic organosiloxane of formula (I) is selected from the monocyclic organosiloxane of formula (I), wherein subscript n is an integer 3 or 4; each R 1 is independently a (C 2 -C 4 )alkenyl; and each R 2 is (C 1 -C 4 )alkyl; alternatively the monocyclic organosiloxane of formula (I), wherein subscript n is an integer 3 or 4; each R 1 is independently a (C 2 -
  • the (C) EBC polyolefin compound may be a low density polyethylene (LDPE, linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), a polyolefin elastomer, an ethylene/(C 3 -C 40 )alpha-olefin) copolymer, or a combination (e.g., blend or melt mixture) of any two or more thereof.
  • the LDPE may have a density from 0.910 to 0.925 g/cm 3 .
  • the LLDPE may have a density from 0.910 to 0.925 g/cm 3 .
  • the MDPE may have a density from 0.926 to 0.940 g/cm 3 .
  • the HDPE may have a density from 0.941 to 0.990 g/cm 3 .
  • the elastomers based on ethylene copolymers may be selected from the EPR and EBR, alternatively the EPR and EOR, alternatively the EBR and EOR, alternatively EPR, alternatively EBR, alternatively EOR. Examples of such elastomers are ENGAGETM, AFFINITYTM, and INFUSETM polyolefin elastomers available from The Dow Chemical Company.
  • the ethylene/(C 3 -C 20 )alpha-olefin) copolymer may be an ethylene/propylene copolymer or an ethylene/(C 4 -C 20 )alpha-olefin) copolymer as described herein.
  • the ethylene-propylene copolymer (EPP) may be a bipolymer or an ethylene-propylene-diene monomer (EPDM) copolymer.
  • the (C) EBC polyolefin compound may be different than the (A) semi-crystalline polyolefin carrier resin and the (L) ethylene-based polymer additive in at least one characteristic selected from monomer composition, comonomer composition, density, crystallinity, melt index, melt flow rate, number-average molecular weight (M n ), weight-average molecular weight (M w ), molecular weight distribution (M w /M n ), and porosity.
  • the (C) EBC polyolefin compound Prior to the mixing step used to prepare the EBC formulation, the (C) EBC polyolefin compound may be in a divided solid form such as a powder, granules and/or pellets.
  • Optional constituent (additive) (D) flame retardant is a compound that inhibits or delays the spread of fire by suppressing chemical reactions in a flame.
  • flame retardant is (D1) a mineral, (D2) an organohalogen compound, (D3) an (organo)phosphorous compound; (D4) a halogenated silicone; or (D5) a combination of any two or more of (D1) to (D4).
  • (D) is not present in the inventive masterbatch, formulation, and/or product.
  • (D) is present in the inventive masterbatch, formulation, and/or product at a concentration from 0.1 to 20 wt %, alternatively 1 to 10 wt %; and alternatively 5 to 20 wt %; all based on total weight thereof.
  • Optional constituent (additive) (E) antioxidant A compound for inhibiting oxidation of a polyolefin.
  • suitable second antioxidants are polymerized 1,2-dihydro-2,2,4-trimethylquinoline (Agerite MA); tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione (Cyanox 1790); distearyl-3,3-thiodiproprionate (DSTDP); tetrakismethylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane (Irganox 1010); 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine (Irganox 1024); bis(4,6-dimethylphenyl)isobutylidene (Lowinox 221646); and 4,4-thi
  • (E) is not present in the inventive masterbatch, formulation, and/or product. In some aspects (E) is present in the inventive masterbatch, formulation, and/or product at a concentration of from 0.01 to 10 wt %, alternatively 0.05 to 5 wt %, alternatively 0.1 to 3 wt %, based on total weight thereof.
  • Optional constituent (additive) (F) processing aid may improve flow of a melt of the coagent masterbatch through a machine.
  • (F) may be an organic processing aid such as a fluoropolymer or a silicone processing aid such as a polyorganosiloxane or fluoro-functionalized polyorganosiloxane.
  • an organic processing aid such as a fluoropolymer or a silicone processing aid such as a polyorganosiloxane or fluoro-functionalized polyorganosiloxane.
  • F is not present in the inventive masterbatch, formulation, and/or product.
  • (F) is present in the inventive masterbatch, formulation, and/or product at a concentration of from 1 to 20 wt %, alternatively 2 to 18 wt %, alternatively 3 to 15 wt %, based on total weight thereof.
  • Optional constituent (additive) (G) a colorant.
  • a colorant E.g., a pigment or dye.
  • the carbon black may be provided as a carbon black masterbatch that is a formulation of poly(l-butene-co-ethylene) copolymer (from ⁇ 95 wt % to ⁇ 100 wt % of the total weight of the masterbatch) and carbon black (from >0 wt % to ⁇ 5 wt % of the total weight of the carbon black masterbatch.
  • colorant is present in the inventive masterbatch, formulation, and/or product at from 0.1 to 35 wt %, alternatively 1 to 10 wt %, based on total weight thereof.
  • Optional constituent (additive) (H) a metal deactivator.
  • OABH oxaylyl bis(benzylidene hydrazide)
  • H is not present in the inventive masterbatch, formulation, and/or product.
  • H is present in the inventive masterbatch, formulation, and/or product at from 0.001 to 0.2 wt %, alternatively 0.01 to 0.15 wt %, alternatively 0.01 to 0.10 wt %, all based on total weight thereof.
  • Optional constituent (additive) (I) (unsaturated carbon-carbon bond)-free hydrolyzable silane. Useful for scavenging moisture.
  • Constituent (I) may be any monosilane containing at least 1, alternatively at least 2, alternatively at least 3, alternatively 4 hydrolyzable groups (e.g., R 2 as defined above); and at most 3, alternatively at most 2, alternatively at most 1, alternatively 0 non-hydrolyzable (unsaturated carbon-carbon bond)-free groups such as alkyl or aryl groups.
  • Examples of (I) are acetoxytrimethylsilane, 4-benzylphenylsulfonoxytributylsilane, dimethylamino-methoxy-dioctylsilane, octyltrimethoxysilane, and tetramethoxysilane.
  • (I) is not present in the inventive masterbatch, formulation, and/or product.
  • (I) is present in the inventive masterbatch, formulation, and/or product at from 0.1 to 2 wt %, alternatively 0.1 to 1.5 wt %, alternatively 0.1 to 1.0 wt %; all based on total weight thereof.
  • Optional constituent (additive) (J) a corrosion inhibitor.
  • tin (II) sulfate a corrosion inhibitor.
  • tin (II) sulfate a corrosion inhibitor.
  • II tin
  • J is not present in the inventive masterbatch, formulation, and/or product.
  • J is present in the inventive masterbatch, formulation, and/or product at from 0.00001 to 0.1 wt %, alternatively 0.0001 to 0.01 wt %, based on total weight thereof.
  • Optional constituent (additive) (K) hindered amine light stabilizer.
  • the (K) is a compound that inhibits oxidative degradation.
  • suitable (K) are butanedioic acid dimethyl ester, polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-ethanol (CAS No.
  • (K) is present in the inventive masterbatch, formulation, and/or product at from 0.001 to 0.2 wt %, alternatively 0.01 to 0.15 wt %, alternatively 0.01 to 0.10 wt %, all based on total weight thereof.
  • Optional constituent (additive) (L) ethylene-based copolymer additive.
  • the constituent (L) is different than constituents (A) and (C).
  • (L) is an LDPE, an ethylene/alpha-olefin copolymer, an ethylene/unsaturated carboxylic ester copolymer (e.g., ethylene/vinyl acetate (EVA) copolymer, ethylene/ethyl acrylate (EEA) copolymer, or ethylene/ethyl methacrylate (EEMA) copolymer).
  • EEMA ethylene/ethyl methacrylate copolymer
  • (L) is not present in the inventive masterbatch, formulation, and/or product.
  • (L) is present in the inventive masterbatch, formulation, and/or product at a concentration from 0.1 to 20 wt %, alternatively 1 to 10 wt %; and alternatively 5 to 20 wt %; all based on total weight thereof.
  • inventive masterbatch, formulation, and/or product does not contain any optional constituents. In some aspects the inventive masterbatch, formulation, and/or product does not contain any optional constituents other than constituents (D) to (L). In some aspects the inventive masterbatch, formulation, and/or product further contains at least one optional constituent (additive) in addition to or in place of (D) to (L). For example, a lubricant or an anti-blocking agent.
  • Any optional constituent may be useful for imparting at least one characteristic or property to the inventive masterbatch, formulation, and/or product in need thereof.
  • the characteristic or property may be useful for improving performance of the inventive masterbatch, formulation, and/or product in operations or applications wherein the inventive masterbatch, formulation, and/or product is exposed to elevated operating temperature.
  • Such operations or applications include melt mixing, extrusion, molding, hot water pipe, and insulation layer of an electrical power cable.
  • the (C 3 )alpha-olefin is 1-propene and its R group in formula (I) is methyl.
  • the (C 2 -C 18 )alkyl group is a monovalent unsubstituted saturated hydrocarbon having from 2 to 18 carbon atoms.
  • Examples of (C 2 -C 18 )alkyl are ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl.
  • the (0 4 -C 20 )alpha-olefin is 1-butene, 1-hexene, or 1-octene; alternatively 1-butene, 1-hexene, or 1-octene; alternatively 1-butene or 1-hexene; alternatively 1-butene or 1-octene; alternatively 1-hexene or 1-octene; alternatively 1-butene; alternatively 1-hexene; alternatively 1-octene; alternatively a combination of any two of 1-butene, 1-hexene, and 1-octene.
  • Any compound herein includes all its isotopic forms, including natural abundance forms and/or isotopically-enriched forms, which may have additional uses, such as medical or anti-counterfeiting applications.
  • the method may comprise electron-beam irradiating the EBC formulation with an effective dose of electron-beam irradiation.
  • the effective dose of electron-beam irradiation may be from 49 to 201 kilojoules energy per kilogram of EBC formulation (kJ/kg), alternatively from 49 to 160 kJ/kg, alternatively from 80 to 201 kJ/kg, alternatively from 80 to 160 kJ/kg, alternatively from 50 to 80 kJ/kg, alternatively from 100 to 140 kJ/kg, alternatively from 160 to 201 kJ/kg.
  • the electron-beam irradiation may be produced using an E-beam accelerator machine such as an Aibang AB5.0 machine available from Wuxi Aibang Radiation Technology Company, Limited, People's Republic of China.
  • the electron-beam irradiating step may be conducted at any suitable temperature such as from 10° to 50° C. (e.g., 23° C. ⁇ 1° C.), under any suitable atmosphere such as air or molecular nitrogen gas, and for any suitable length of time such as from 0.1 to 20 minutes, alternatively from 0.1 to 10 minutes, alternatively from 0.1 to 5 minutes.
  • the irradiation may be dosed continuously or intermittently, alternatively continuously.
  • ASTM means the standards organization, ASTM International, West Conshohocken, Pennsylvania, USA.
  • IEC means the standards organization, International Electrotechnical Commission, Geneva, Switzerland. Any comparative example is used for illustration purposes only and shall not be prior art. Free of or lacks means a complete absence of; alternatively not detectable.
  • IUPAC International Union of Pure and Applied Chemistry (IUPAC Secretariat, Research Triangle Park, N.C., USA). May confers a permitted choice, not an imperative. Operative means functionally capable or effective. Optional(ly) means is absent (or excluded), alternatively is present (or included).
  • PPM are weight based.
  • Ranges include endpoints, subranges, and whole and/or fractional values subsumed therein, except a range of integers does not include fractional values.
  • Room temperature is 23° C. ⁇ 1° C.
  • Substituted when referring to a compound means having, in place of hydrogen, one or more substituents, up to and including per substitution.
  • Comonomer composition distribution may be characterized by the CDBI Method.
  • CDBI Comonomer Distribution Breadth Index
  • Crystallinity Test Method For determining crystallinity in wt % of a semi-crystalline polyolefin resin such as (A) semi-crystalline polyolefin carrier resin. Determine melting peaks and weight percent (wt %) crystallinity using DSC instrument DSC Q1000 (TA Instruments) as follows. Procedure (A) Baseline calibrate instrument. Use software calibration wizard. First obtain a baseline by heating a cell from ⁇ 80° to 280° C. without any sample in an aluminum DSC pan. Then use sapphire standards as instructed by the calibration wizard. The analyze 1 to 2 milligrams (mg) of a fresh indium sample by heating the standards sample to 180° C., cooling to 120° C.
  • mg milligrams
  • H f cool curve heat of fusion
  • Density Test Method measured according to ASTM D792-13, Standard Test Methods for Density and Specific Gravity ( Relative Density ) of Plastics by Displacement , Method B (for testing solid plastics in liquids other than water, e.g., in liquid 2-propanol). Report results in units of grams per cubic centimeter (g/cm 3 ).
  • the lower the level of crosslinking in the test sample the greater the extent of elongation thereof in the Hot Creep Test Method. Conversely, the higher the level of crosslinking in the test sample, the lesser the extent of elongation thereof. If the level of crosslinking in the test sample is low enough, the test sample can fail by breaking, which may occur within a few minutes or even seconds of start of its testing run. Although power cables may not experience operating temperatures as high as 200° C., this test is a reliable way for the industry to evaluate materials for use in insulation layers thereof. The lower the hot creep percent, the better the performance of the material. In the power cable industry, a hot creep of less than 175% after the test sample has been held for 15 minutes at 200° C.
  • test sample passes the hot creep test. And a hot creep of less than 100% after 15 minutes at 200° C. is especially desirable. If the test sample is intact after 15 minutes, the weight is removed, the test sample is removed from the oven and allowed to cool to room temperature. Residual elongation of the test sample after cooling is measured. For a power cable, the residual elongation at room temperature should be less than 15% of the hot creep value measured at 200° C.
  • Sweat Out Test Method (Qualitative): prepare HDPE pellets containing coagent as described later for the inventive masterbatch examples (e.g., IE1 to IE4). Prepare LLDPE pellets containing coagent as described later for comparative EBC formulations CE1 to CE5. Add each pellets sample to a separate, unused press-sealed polyethylene plastic bag (also known as zip lock or click seal bags). Seal bags. Press pellets in bags. Store bags and contents at room temperature for 14 days. At 14 days observe bags for oil traces left over on the bags' surfaces under light. Oil trace indicates surface migration and poor solubility. More oil trace on surface of bag, more TAIC sweat-out. Rank progressive amount of sweat out by characterizing the oil trace as none, very little, little, or obvious (more than a little).
  • Sweat Out Test Method prepare HDPE pellets or LLDPE pellets as described above for the qualitative test method. Using thermogravimetric analysis (TGA) measure the initial loading of coagent on a freshly prepared pellet. Each pellet weighs 20 to 30 mg and is approximately dimensioned 4 mm ⁇ 2.5 mm in volume. Store the pellets for 20 days at room temperature. At 20 days, wash a sample of the stored pellets with acetonitrile (ACN) as per the following procedure: (1) weigh 3.000 g ⁇ 0.001 g of pellets sample into a 40 mL vial. (2) Feed 14.5 mL of ACN into the 40 mL vial.
  • TGA thermogravimetric analysis
  • Semi-crystalline polyolefin carrier resin (A1) a HDPE having a density of 0.965 g/cc 3 , a melt index (I 2 ) of 7.5 to 8.5 g/10 min.; and a monomodal MWD.
  • resin (A1) had a second heating curve heat of fusion ( ⁇ H f ) of 223.7 J/g, and a corresponding crystallinity of 76.6 wt %.
  • Alkylene-functional coagent (B1) triallyl isocyanurate (TAIC).
  • Alkenyl-functional coagent (B3) trimethylolpropane trimethylacrylate (“TMPTMA”).
  • EBC polyolefin compound (C1) an ethylene/1-butene LLDPE (C1), stabilized with metal deactivator (H1) oxaylyl bis(benzylidene hydrazide (OABH) and two antioxidants, and has a density of 0.921 g/cc 3 , melt index (I 2 ) of 0.7 g/10 min., and a monomodal MWD. Available as pellets as product DFDA-7540 NT from The Dow Chemical Company.
  • H1 metal deactivator oxaylyl bis(benzylidene hydrazide
  • Comparative Examples 1 and 2 two comparative EBC formulations are prepared by soaking LLDPE (C1) pellets with one of coagent (B1) 80° C. for 6 hours in an oven to allow coagent to penetrate into the LLDPE pellets.
  • Comparative Examples 3 to 5 (CE3 to CE5): three comparative EBC formulations are prepared separately by compounding. Feed LLDPE (C1) to a Brabender mixer at 120° C. Allow the LLDPE (C1) to melt completely at a rotor speed of 35 rotations per minute (rpm). Then gradually add one of coagents (B2) to (B4), respectively, over 15 minutes, and melt mix the resulting mixture at 35 rpm for 4 minutes. Then stop the rotation, remove the mixed EBC formulation (one of CE3 to CE5) from the Brabender mixer. Promptly hot press the formulation at 120° C. to shape the formulation CE3, CE4, or CE5 as a 1-millimeter (mm) thick sheet.
  • Comparative Examples 6 and 7 comparative cured polyolefin products prepared by separately hot pressing the formulation CE1 or CE2 at 120° C. to shape the formulation CE1 or CE2 as a 1-mm thick sheet, and then curing the sheet EBC formulations of CE1 and CE2, respectively, with 100 kilojoules per kilogram (kJ/kg) irradiation dose of electron-beam.
  • inventive cured polyolefin products prepared by curing the EBC formulations EBCF1 and EBCF2 of IE5 and IE6, respectively, with 100 kilojoules per kilogram (kJ/kg) irradiation dose of electron-beam.
  • compositions Inventive Coagent Masterbatches MB1 to MB4 of IE1 to IE4, respectively.
  • IE1 IE2 IE3 IE4 HDPE (A1) 85 87 87 87 TAIC (B1) 15 0 0 0 ViD4 (B2) 0 13 0 0 TMPTMA (B3) 0 0 13 0 TAC (B4) 0 0 0 13 Masterbatch 100.00 100.00 100.00 100.00 100.00 100.00 Total wt %
  • the hot creep data in Table 6 show that the inventive EBC formulations, which contain the inventive masterbatch, are significantly better at curing to give inventive cured polyolefin products having improved (decreased) hot creep at 200° C. than are comparative cured polyolefin products prepared from comparative EBC formulations that contain the same alkenyl-functional coagent but do not contain the inventive masterbatch.
  • the TAIC loading in the comparative EBC formulations is lower due to TAIC sweat out limits than is the TAIC loading in the inventive EBC formulations, which do not have such sweat out limits.
  • the higher TAIC loading in the inventive EBC formulations show the beneficial effect of increasing electron-beam curing efficiency of the inventive curing method.

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