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EP-3784725-B1 - POLYOLEFIN ADDITIVE FORMULATIONS

EP3784725B1EP 3784725 B1EP3784725 B1EP 3784725B1EP-3784725-B1

Inventors

  • HAN, SUH JOON
  • KJELLQVIST, JERKER B.L.

Dates

Publication Date
20260506
Application Date
20190425

Claims (10)

  1. A curable polyolefin-additive formulation comprising constituents (A) to (D): from 70 to 99.7 weight percent (wt%) of (A) a polyolefin polymer having a melt index ("I 2 ") of from 0.1 to 50 grams per 10 minutes (g/10 min.), measured by ASTM D1238-04 at 190° C. and load of 2.16 kilograms according to the Melt Index Test Method; from 0.1 to 5 wt% of (B) a carbon black; from 0.2 to 5 wt% of (C) a triazinyl-functional hindered piperidine; and from 0.1 to 1.00 wt% of (D) a sulfur-containing hindered bisphenol (SCHBP) of formula (I): HO(R 1 ) x Ph-S-Ph(R 2 ) y OH (I), wherein subscript x is an integer from 1 to 3; HO(R 1 ) x Ph is a first monovalent hindered phenol group wherein each R 1 is independently a (C 1 -C 7 )alkyl and at least one R 1 is independently a (C 3 -C 6 )alkyl and is ortho to the hydroxyl (HO-) of the first monovalent hindered phenol group; subscript y is an integer from 1 to 3; Ph(R 2 ) y OH is a second monovalent hindered phenol group wherein each R 2 is independently a (C 1 -C 7 )alkyl and at least one R 2 is independently a (C 3 -C 6 )alkyl and is ortho to the hydroxyl (-OH) of the second monovalent hindered phenol group; and wherein the (B) carbon black is characterized by (i) a particle size from 15 to 30 nanometers (nm) measured according to ASTM D3849-14a; and (ii) an oil absorption number (OAN) from 50 to 250 milliliters per 100 grams (ml/100 g) measured according to ASTM D2414-17, Procedure A with dibutyl phthalate (DBP).
  2. The curable polyolefin-additive formulation of claim 1 wherein the (A) polyolefin polymer is characterized by any one of limitations (i) to (xv): (i) an ethylene-based polymer; (ii) an ethylene-based polymer that is a low density polyethylene (LDPE); (iii) an ethylene-based polymer that is a linear low density polyethylene (LLDPE); (iv) an ethylene-based polymer that is a medium density polyethylene (MDPE); (v) an ethylene-based polymer that is a high density polyethylene (HDPE); (vi) an ethylene-based polymer that is a poly(ethylene-co-alpha-olefin) copolymer; (vii) is a polypropylene; (viii) an ethylene-based polymer that is an ethylene/propylene copolymer; (ix) a density of at least 0.925 g/cm 3 and is a polyethylene and has a melt flow index (I 2 ) of 0.1 to 20 g/10 min. at 190° C./2.16 kg load; (x) a density of 0.89 to 0.96 g/cm 3 and is a polypropylene and has a melt flow rate (MFR) of 0.5 to 50 g/10 min. at 230° C./2.16 kg load; (xi) a molecular weight distribution (MWD) that is monomodal; (xii) a MWD that is bimodal; (xiii) a combination of (ii) and (ix); (xiv) a combination of (ii), (ix) and (xi); and (xv) a combination of (ii), (ix) and (xii).
  3. The curable polyolefin-additive formulation of any one of claims 1 or 2 wherein the (C) triazinyl-functional hindered piperidine is selected from (i) a mixture of 1,3,5-Triazine-2,4,6-triamine, N,N'-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1propanediyl]]-bis[N,N'-dibutyl-N,N'-bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-, and dimethyl succinate polymer with 4-hydroxy-2,2,6,6,-tetramethyl-1-piperidineethanol; (ii) (poly[[6-(1,1,3,3-tetramethylbutyl) amino]-1,3,5-triazine-2,4-diyl][[2,2,6,6-tetramethyl-4-piperidyl)imino]]hexamethylene (2,2,6,6-tetramethyl-4-piperidyl)imino]]); (iii) (1,3,5-Triazine-2,4,6-triamine-N,N'-[1,2-ethanediylbis[[[4. 6-bis[butyl(1,2,2,6,6-pentamethyl-4-peperidinyl)amino]-1,3,5-triazin-2-yl] imino]-3,1-propanediyl]]-bis[N,N'-dibutyl-N,N'-bis (1,2,2,6,6-pentamethyl-4-piperidinyl); and (iv) a reaction product of 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-polymer with 2,4,6-trichloro-1,3,5-triazine with N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine.
  4. The curable polyolefin-additive formulation of any one of claims 1 to 3 wherein the (D) SCHBP is characterized by any one of limitations (i) to (ix): (i) subscript x is 2 or 3; (ii) at least one R 1 is a 1,1-dimethylethyl and is ortho to the hydroxyl of the first monovalent hindered phenol group; (iii) subscript y is 2 or 3; (iv) at least one R 2 is a 1,1-dimethylethyl and is ortho to the hydroxyl of the second monovalent hindered phenol group; (v) at least one R 1 is a 1,1-dimethylethyl and is ortho to the hydroxyl of the first monovalent hindered phenol group and at least one R 1 is a methyl; (vi) at least one R 2 is a 1,1-dimethylethyl and is ortho to the hydroxyl of the second monovalent hindered phenol group and at least one R 2 is a methyl; (vii) subscript x is 2, one R 1 is a 1,1-dimethylethyl and is ortho to the hydroxyl of the first monovalent hindered phenol group and one R 1 is a methyl; (viii) subscript y is 2, one R 2 is a 1,1-dimethylethyl and is ortho to the hydroxyl of the second monovalent hindered phenol group and one R 2 is a methyl; and (ix) the SCHBP is 4,4'-thiobis(2-(1,1-dimethylethyl)-5-methylphenol).
  5. The curable polyolefin-additive formulation of any one of claims 1 to 4 further comprising at least one additive selected from 0.1 to 5 wt% of (E) an organic peroxide; (F) an antioxidant having a structure different than formula (I); (G) a processing aid; (H) a colorant; (I) a metal deactivator; (J) an olefin-functional hydrolyzable silane; (K) a corrosion inhibitor; (L) a flame retardant; and (M) a filler.
  6. The curable polyolefin-additive formulation of any one of claims 1 to 4 further comprising from 0.1 to 5 wt% of (E) an organic peroxide and/or (J) an olefin-functional hydrolyzable silane.
  7. A method of making a curable polyolefin-additive formulation, the method comprising mixing the constituents (A) to (D) of any one of claims 1 to 4 and optionally any one or more of constituents (E) to (M) of claim 5 or 6 so as to give a mixture; and melting or extruding the mixture so as to make the curable polyolefin-additive formulation.
  8. A crosslinked polyolefin-additive product comprising a reaction product of curing the curable polyethylene-additive formulation of any one of claims 1 to 6.
  9. A manufactured article comprising a shaped form of the crosslinked polyolefin-additive product of claim 8.
  10. 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 curable polyethylene-additive formulation of any one of claims 1 to 6 or the crosslinked polyolefin-additive product of claim 8.

Description

FIELD Polyolefin-additive formulations, products, articles and related methods. INTRODUCTION Patents in the field include CN 103509239 B, US 5,380,591; US 5,766,761; US 6,468,583 B1; and US 6,656,986 B2. Insulated electrical conductors typically comprise a conductive core covered by an insulation layer. The conductive core may be solid or stranded (e.g., a bundle of wires). Some insulated electrical conductors may also contain one or more additional elements such as semiconducting layer(s) and/or a protective jacket (e.g., wound wire, tape, or sheath). Examples are coated metal wires and electrical power cables, including those for use in low voltage ("LV", > 0 to < 5 kilovolts (kV)), medium voltage ("MV", 5 to < 69 kV), high voltage ("HV", 69 to 230 kV) and extra-high voltage ("EHV", > 230 kV) electricity-transmitting/distributing applications. Evaluations of power cables may use AEIC/ICEA standards and/or IEC test methods. In the field during operational use, the power cables are exposed to harmful effects of ultraviolet light (e.g., from the sun) and heat up to 90° C. or more (e.g., generated within the cable). SUMMARY We have discovered a need for new materials for use as insulation layers in power cables. The material would exhibit enhanced stability when subjected to a combination of heat and ultraviolet (UV) light and have satisfactory dielectric properties. Our technical solution to this problem inhibits degradations caused by heat and degradations caused by UV light while maintaining satisfactory dielectric properties. The solution includes a curable polyolefin-additive formulation comprising a polyolefin polymer, a carbon black, a hindered amine light stabilizer that is a triazinyl-functional hindered piperidine, and an antioxidant that is a sulfur-containing hindered bisphenol. Also included is a crosslinked polyolefin-additive product made by curing the curable polyolefin-additive formulation. Also included are methods of making and using same, and articles containing or made from same. DETAILED DESCRIPTION Examples of embodiments include the following numbered aspects. Aspect 1. A curable polyolefin-additive formulation comprising constituents (A) to (D): from 70 to 99.7 weight percent (wt%) of (A) a polyolefin polymer having a melt index ("I2") of from 0.1 to 50 grams per 10 minutes (g/10 min.), measured by ASTM D1238-04 at 190° C. and load of 2.16 kilograms according to the Melt Index Test Method (described later); from 0.1 to 5 wt% of (B) a carbon black; from 0.2 to 5 wt%, alternatively 0.25 to 3.4 wt% of (C) a triazinyl-functional hindered piperidine; and from 0.1 to 1.00 wt%, alternatively from 0.1 to 0.90 wt%, alternatively from 0.2 to 0.90 wt% of (D) a sulfur-containing hindered bisphenol (SCHBP) of formula (I): HO(R1)xPh-S-Ph(R2)yOH (I), wherein subscript x is an integer from 1 to 3; HO(R1)xPh is a first monovalent hindered phenol group wherein each R1 is independently a (C1-C7)alkyl and at least one R1 is independently a (C3-C6)alkyl and is ortho to the hydroxyl (HO-) of the first monovalent hindered phenol group; subscript y is an integer from 1 to 3; Ph(R2)yOH is a second monovalent hindered phenol group wherein each R2 is independently a (C1-C7)alkyl and at least one R2 is independently a (C3-C6)alkyl and is ortho to the hydroxyl (-OH) of the second monovalent hindered phenol group; and wherein the (B) carbon black is characterized by (i) a particle size from 15 to 30 nanometers (nm) measured according to ASTM D3849-14a; and (ii) an oil absorption number (OAN) from 50 to 250 milliliters per 100 grams (ml/100 g) measured according to ASTM D2414-17, Procedure A with dibutyl phthalate (DBP). All wt% of constituents of the curable polyolefin-additive formulation are based on total weight of the curable polyolefin-additive formulation. The "polyolefin additive formulation" and "polyolefin-additive formulation" mean the same thing, which is a material or mixture prepared according to a list of ingredients and their amounts. For example, in aspect 1 the list of ingredients comprises the (A) polyolefin polymer and additives (B) to (D) and their amounts are their respective wt%. The polyolefin additive formulation may be curable (e.g., aspects 1 to 6) or crosslinked (e.g., aspect 8). The "curable" means capable of forming or being crosslinked. The "crosslinked" may be a partially networked material, which has some crosslinks between macromolecules and some macromolecules capable of further crosslinking; or a completely networked material, wherein no further crosslinks between macromolecules may be formed (steady state thermoset). Aspect 2. The curable polyolefin-additive formulation of aspect 1 wherein the (A) polyolefin polymer is characterized by any one of limitations (i) to (xv): (i) an ethylene-based polymer; (ii) an ethylene-based polymer that is a low density polyethylene (LDPE); (iii) an ethylene-based polymer that is a linear low density polyethylene (LLDPE); (iv) an ethylene-based