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WO2021053412A1 - High-density polyethylene with additives for increased transparency - Google Patents

High-density polyethylene with additives for increased transparency Download PDF

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Publication number
WO2021053412A1
WO2021053412A1 PCT/IB2020/057291 IB2020057291W WO2021053412A1 WO 2021053412 A1 WO2021053412 A1 WO 2021053412A1 IB 2020057291 W IB2020057291 W IB 2020057291W WO 2021053412 A1 WO2021053412 A1 WO 2021053412A1
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WO
WIPO (PCT)
Prior art keywords
hdpe
composition
ppm
agent
density polyethylene
Prior art date
Application number
PCT/IB2020/057291
Other languages
French (fr)
Inventor
Anantharaman Dhanabalan
Radha Kamalakaran
Maria Soliman
Sadasivam GOPALAKRISHANAN
Jerome VACHON
Original Assignee
Sabic Global Technologies B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sabic Global Technologies B.V. filed Critical Sabic Global Technologies B.V.
Publication of WO2021053412A1 publication Critical patent/WO2021053412A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised 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
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised 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
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/062HDPE
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)

Definitions

  • the invention relates to high-density polyethylene compositions that have improved transparency and/or reduced haze.
  • HDPE high-density polyethylene
  • ESCR mechanical and environmental stress cracking resistance
  • a high-density polyethylene (HDPE) composition having increased transparency and/or reduced haze comprises a mixture of a HDPE, a monomeric and/or polymeric additive that is partially and/or fully dispersed within the HDPE, and a clarifying and/or nucleating agent in an amount of 50 ppm to 500 ppm by total weight of the HDPE composition.
  • the HDPE composition has at least one of a transparency of from 80% or more and a haze of from 60% or less as determined by ASTM D1003 at a thickness of from 1 mm or more.
  • the HDPE composition may have at least one of a transparency of from 90% or more and a haze of from 50% or less as determined by ASTM D1003 at a thickness of from 1 mm or more, without drawing, stretching or orienting the HDPE composition.
  • the HDPE may be at least one of a unimodal, bimodal, and multimodal HDPE.
  • Mw average molecular weight
  • MFR melt flow rate
  • the monomeric and/or polymeric additive may be present in an amount of from 0.1 wt.% to 5 wt.% by total weight of the HDPE composition.
  • the monomeric and/or polymeric additive is selected from at least one of a monomeric phase change material, methyl laurate, 1-decanol and tetradecane, a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a branched polyethylene, a low molecular weight high density polyethylene, an ultrahigh molecular weight polyethylene (UHMWPE), a polyolefin elastomer (POE), a polyolefin plastomer (POP), maleic anhydride grafted polyethylene, and combinations thereof.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • UHMWPE ultrahigh molecular weight polyethylene
  • POE polyolefin elastomer
  • POP polyolefin plastomer
  • the clarifying and/or nucleating agent may be present in an amount of 100 ppm to 200 ppm by total weight of the HDPE composition.
  • the clarifying and/or nucleating agent may be selected from at least one of a sorbitol derivative, 1,2,3,4-bis-dibenzylidene sorbitol (DBS), l,2,3,4-bis-(p-methoxybenzylidene sorbitol) (DOS), l,2,3,4-bis-(3,4-dimethylbenzylidene sorbitol) (MBDS), and l,3:2,4-di(3,4-dimethylbenzylidene) sorbitol (DMDBS), a calcium salt of dicarboxylic acid, a metal salt of cyclohexane dicarboxylic acid, a bisamide, a lithium carbonate, a benzoic acid, an inorganic oxide, nano-zinc oxide, talc, clay, a powdere
  • the HDPE may be a copolymer with comonomers selected from C3 to C10 olefin monomers, the comonomers being present in the HDPE copolymer in an amount of from 2 wt.% or less.
  • the HDPE composition may further include one or more of a heat conductive agent, a tie agent, an antiblocking agent, an antistatic agent, an antioxidant, a neutralizing agent, an acid scavenger, a blowing agent, a crystallization aid, a dye, a flame retardant agent, a filler, a hard filler, a soft filler, an impact modifier, a mold release agent, an oil, another polymer, a pigment, a processing agent, a reinforcing agent, a stabilizer, a light stabilizer, an UV resistance agent, a slip agent, a flow modifying agent, and combinations thereof.
  • the HDPE composition may be formed into an article of manufacture.
  • the article may be one or more of a film, a molded part, a container, a beverage container cap, a lid, a sheet, a pipe, a pipe coupling, a bottle, a cup, a tray, a pallet, and a toy.
  • the article may be formed by injection molding, blow molding, compression molding, sheet extrusion, film blowing, pipe extrusion, profile extrusion, calendaring, or thermoforming.
  • a high-density polyethylene (HDPE) composition having increased transparency and/or reduced haze comprises a mixture of a HDPE, a monomeric and/or polymeric additive that is partially and/or fully dispersed within the HDPE in an amount of from 0.1 wt.% to 5 wt.% by total weight of the HDPE composition.
  • the HDPE composition further includes a clarifying and/or nucleating agent in an amount of 100 ppm to 500 ppm by total weight of the HDPE composition.
  • the HDPE composition has a transparency of from 80% or more and/or a haze of from 40% or less as determined by ASTM D1003 at a thickness of from 1 mm or more, without drawing, stretching or orienting the HDPE composition.
  • the monomeric and/or polymeric additive is selected from at least one of a monomeric phase change material, methyl laurate, 1-decanol and tetradecane, a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a branched polyethylene, a low molecular weight high density polyethylene, an ultrahigh molecular weight polyethylene (UHMWPE), a poly olefin elastomer (POE), a poly olefin plastomer (POP), maleic anhydride grafted polyethylene, and combinations thereof.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • UHMWPE ultrahigh molecular weight polyethylene
  • POE poly olefin elastomer
  • POP poly olefin plastomer
  • maleic anhydride grafted polyethylene and combinations thereof.
  • the clarifying and/or nucleating agent is selected from at least one of a sorbitol derivative, 1,2,3,4-bis-dibenzylidene sorbitol (DBS), l,2,3,4-bis-(p-methoxybenzylidene sorbitol) (DOS), l,2,3,4-bis-(3,4-dimethylbenzylidene sorbitol) (MBDS), and l,3:2,4-di(3,4- dimethylbenzylidene) sorbitol (DMDBS), a calcium salt of dicarboxylic acid, a metal salt of cyclohexane dicarboxylic acid, a bisamide, a lithium carbonate, a benzoic acid, an inorganic oxide, nano-zinc oxide, talc, clay, powdered polymeric agents such as polyphenylene oxide, polyvinylenedifluoride, polycarbonate, polycarbonate- siloxane copolymer,
  • the clarifying and/or nucleating agent is present in an amount of 100 ppm to 200 ppm by total weight of the HDPE composition.
  • the HDPE may be at least one of a unimodal, bimodal, and multimodal HDPE.
  • the polymer blend may be formed into an article of manufacture.
  • the article may be a film, a molded part, a container, a bottle, a beverage container cap, a lid, a sheet, a pipe, a pipe coupling, a bottle, a cup, a tray, a pallet, and a toy.
  • a HDPE high-density polyethylene
  • a HDPE is modified by combining the HDPE with a monomeric and/or polymeric additive that is partially and/or fully dispersed within the HDPE, and a clarifying and/or nucleating agent in an amount of 100 ppm to 500 ppm by total weight of the HDPE composition so that the HDPE composition has at least one of a transparency of from 80% or more and a haze of from 60% or less as determined by ASTM D1003 at a thickness of from 1 mm or more.
  • a monomeric and/or polymeric additive that is partially and/or fully dispersed within the HDPE
  • a clarifying and/or nucleating agent in an amount of 100 ppm to 500 ppm by total weight of the HDPE composition so that the HDPE composition has at least one of a transparency of from 80% or more and a haze of from 60% or less as determined by ASTM D1003 at a thickness of from 1 mm or more.
  • the present invention is related to the development of high-density polyethylene (HDPE) compositions, which may be used in various applications, such as blow/injection/compression moldable applications, with improved transparency.
  • HDPE high-density polyethylene
  • This includes several packaging applications, including caps and closures, trays, pipes, toys, chemical containers, shampoo bottles, milk jugs, recycling bins, and industrial bulk containers.
  • caps and closures trays, pipes, toys, chemical containers, shampoo bottles, milk jugs, recycling bins, and industrial bulk containers.
  • an enhanced optically transparent plastic becomes more vital. Bottles that are less opaque than those traditionally used have been placed on the market recently. The use of bottles having greater clarity can be aesthetically appealing to consumers.
  • Transparent bottles may also be appealing to consumers during use as it enables the consumer to ascertain easily how much product remains.
  • the reduction of total haze of molded parts, as demanded by the consumers, while maintaining the inherent mechanical strength and processability of the HDPE is an emerging challenge.
  • the transparent HDPE composition is envisaged to have light weight and higher impact resistance.
  • the transparent HDPE composition is envisaged to have better hydrolytic stability and moisture barrier resistance, as compared to transparent polymers such as polycarbonate and polymethylmethacrylate.
  • the transparency of HDPE can be increased by incorporating various optics-enhancing additives. Additionally, the total haze of the HDPE can be reduced by the use of such optics-enhancing additives.
  • These optics-enhancing additives are incorporated into a unimodal, bimodal or multimodal HDPE, or a blend of these, by melt blending the optics-enhancing additives with the HDPE. The amount and the type of the optics enhancing additives incorporated into the HDPE is selected so that the processability of the HDPE remains relatively unaffected while its transparency and/or reduction in haze is enhanced.
  • the HDPE polymers used in the polymer blend can include those prepared by any of the polymerization processes, which are in commercial use (e.g., a “high pressure” process, a slurry process, a solution process and/or a gas phase process) and with the use of any of the known catalysts (e.g., multisite catalysts such as Ziegler Natta catalysts, and/or single site catalysts such as chromium or Phillips catalysts, metallocene catalysts, and the like).
  • a “high pressure” process e.g., a “high pressure” process, a slurry process, a solution process and/or a gas phase process
  • the known catalysts e.g., multisite catalysts such as Ziegler Natta catalysts, and/or single site catalysts such as chromium or Phillips catalysts, metallocene catalysts, and the like.
  • high-density polyethylene or “HDPE”
  • All or a major portion of the HDPE component may be unimodal or bimodal HDPE, either alone or as a blend.
  • the unimodal and/or hi modal HDPE or combination of such HDPE materials may make up from 50 wt.% or greater of the HDPE component or from 50 wt.% to 100 wt.% of the HDPE component.
  • the HDPE component may comprise unimodal and/or hi modal HDPE in an amount of from at least, equal to, and/or between any two of 50 wt.%, 51 wt.%, 52 wt.%, 53 wt.%, 54 wt.%, 55 wt.%, 56 wt.%, 57 wt.%, 58 wt.%, 59 wt.%, 60 wt.%, 61 wt.%, 62 wt.%, 63 wt.%, 64 wt.%, 65 wt.%, 66 wt.%, 67 wt.%, 68 wt.%, 69 wt.%, 70 wt.%, 71 wt.%, 72 wt.%, 73 wt.%, 74 wt.%, 75 wt.%, 76 wt.%,
  • the HDPE component may comprise unimodal and/or hi modal HDPE in an amount of from 80 wt.% to 100 wt.%. If less than 100 wt.% of unimodal and/or hi modal HDPE is used for the HDPE component, the remainder may be made up of multimodal HDPE.
  • the polymer blends of the present invention do not include polypropylene.
  • all or a major portion of the HDPE component may be multimodal HDPE.
  • the multimodal HDPE may make up from 50 wt.% or greater of the HDPE component or from 50 wt.% to 100 wt.% of the HDPE component.
  • the HDPE component may comprise multimodal HDPE in an amount of from at least, equal to, and/or between any two of 50 wt.%, 51 wt.%, 52 wt.%, 53 wt.%, 54 wt.%, 55 wt.%, 56 wt.%, 57 wt.%, 58 wt.%, 59 wt.%, 60 wt.%, 61 wt.%, 62 wt.%, 63 wt.%, 64 wt.%, 65 wt.%, 66 wt.%, 67 wt.%, 68 wt.%, 69 wt.%, 70 wt.%, 71 wt.%, 72 wt.%, 73 wt.%, 74 wt.%, 75 wt.%,
  • the HDPE component may comprise multimodal HDPE in an amount of from 80 wt.% to 100 wt.%. If less than 100 wt.% of multimodal HDPE is used for the HDPE component, the remainder may be made up of unimodal and/or bimodal HDPE. If less than 100 wt.% of unimodal and/or hi modal HDPE is used for the HDPE component, the remainder may be made up of multimodal HDPE.
  • the polymer blends of the present invention do not include polypropylene.
  • the HDPE component of the polymer blend will constitute homopolymers of ethylene. These may include homopolymers solely of neat HDPE.
  • the HDPE component can include copolymers of ethylene with at least one C3 to C10 alpha olefin. Typically, this will be at least one of the alpha olefins of butene, hexene, and/or octene.
  • the HDPE is a copolymer with 1 -butene (polyethylene- 1 -butene) or 1 -hexene (polyethylene- 1 -hexene).
  • the non ethylene comonomer may be present in the HDPE copolymer in an amount of from 2 wt.%, 1.5 wt.%, 1 wt.%, 0.5 wt.%, 0.1 wt.% or less. In particular embodiments, there is no butene or no C3 to C10 alpha olefin comonomer.
  • Those amount percentages of multimodal HDPE, hi modal HDPE, and/or unimodal HDPE presented previously for the HDPE component may include such HDPE incorporating such copolymers.
  • the main HDPE component may be an un-functionalized neat HDPE with no functional groups along the polymer chain.
  • the HDPE contains anhydride modified HDPE as an additive which is present in an amount of from 2 wt.%, 1.5 wt.%, 1 wt.%, 0.5 wt.%, 0.1 wt.% or less.
  • the HDPE can be characterized by various properties such as average molecular weight, poly dispersity index, density, the melt flow rates (MFR), ESCR, tensile strength at yield, tensile modulus, tensile elongation at yield, Izod notched impact strength, hardness or combinations thereof.
  • MFR melt flow rates
  • ESCR tensile strength at yield
  • tensile modulus tensile modulus
  • tensile elongation at yield Izod notched impact strength
  • hardness or combinations thereof tensile strength at yield
  • MFR melt flow rates
  • Mw melt flow rates
  • the average molecular weight (Mw) of the HDPE may be from at least, equal to, and/or between any two of 130,000, 140,000, 150,000, 160,000, 170,000, 180,000, 190,000, 200,000, 210,000, 220,000, 230,000, 240,000, 250,000, 260,000, 270,000, 280,000, 290,000, and 300,000 as determined by high temperature gel permeation chromatography. Unless otherwise specified, all average molecular weights (Mw) for those polymers described herein are those determined by high temperature gel permeation chromatography.
  • the density of the HDPE can be from 940 kg/m 3 or 945 kg/m 3 to 965 kg/m 3 .
  • the density of the HDPE may be from at least, equal to, and/or between any two of
  • the density of the HDPE may range from 955 kg/m 3 to 965 kg/m 3 .
  • the HDPE can have a MFR at 190 °C and 5 kg of from 0.1 g/10 min to 20 g/10 min as per ISO 1133, or at least, equal to, and/or between any two of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1.0 g/10 min, 1.1 g/10 min, 1.2 g/10 min, 1.3 g/10 min, 1.4 g/10 min, 1.5 g/10 min, 1.6 g/10 min, 1.7 g/10 min, 1.8 g/10 min, 1.9 g/10 min, 2.0 g/10 min, 2.1 g/10 min, 2.2 g/10 min, 2.3 g/10 min, 2.4 g/10 min, 2.5 g/10 min, 2.6 g/10 min, 2.7 g/10 min, 2.8 g/10 min, 2.9 g/10 min, 2.0
  • the HDPE may have an MFR at 190 °C and 5 kg of from 0.5 g/10 min to 5 g/10 min.
  • the HDPE may have a MFR at 190 °C and 2.16 kg of from 0.1 g/10 min to 5.0 g/10 min, as per ISO 1133, or at least, equal to, and/or between any two of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1.0 g/10 min, 1.1 g/10 min, 1.2 g/10 min, 1.3 g/10 min, 1.4 g/10 min,
  • the HDPE may have a MFR at 190 °C and 21.6 kg of from 10 g/10 min to 35 g/10 min, as per ISO 1133, or at least, equal to, and/or between any two of 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min,
  • Tensile modulus of the HDPE can be from 800 MPa to 1300 MPa, or at least, equal to, and/or between any two of 800 MPa, 850 MPa, 900 MPa, 950 MPa, 1000 MPa, 1050 MPa, 1100 MPa, 1150 MPa, 1200 MPa, 1250 MPa and 1300 MPa, as measured by ISO 527.
  • Tensile strength at yield of the HDPE can be from 20 MPa to 40 MPa, or at least, equal to, and/or between any two of 20 MPa, 25 MPa, 30 MPa, 35 MPa, and 40 MPa, as measured by ISO 527.
  • the Izod notched impact strength of the HDPE component at -30 °C can be from 3 kJ/m 2 to 6 kJ/m 2 or at least, equal to, and/or between any two of 3 kJ/m 2 , 4 kJ/m 2 , 5 kJ/m 2 , and 6 kJ/m 2 .
  • the Izod notched impact strength of the HDPE component at 23 °C can be from 10 kJ/m 2 to 22 kJ/m 2 or at least, equal to, and/or between any two of 10 kJ/m 2 , 11 kJ/m 2 , 12 kJ/m 2 , 13 kJ/m 2 , 14 kJ/m 2 , 15 kJ/m 2 , 16 kJ/m 2 , 17 kJ/m 2 , 18 kJ/m 2 , 19 kJ/m 2 , 20 kJ/m 2 , 21 kJ/m 2 22 kJ/m 2 , 23 kJ/m 2 , 24 kJ/m 2 , 25 kJ/m 2 , 26 kJ/m 2 , 27 kJ/m 2 , 28 kJ/m 2 , 29 kJ/m 2 and 30 kJ/m 2 as measured by ISO 180.
  • the HDPE component as described above, is used as a polymer blend in combination with one or more different optics-enhancing additives used to provide the increased transparency and/or reduced haze.
  • the lack of transparency and/or haze of HDPE is the result of light scattering that results in the opaque or translucent appearance of the HDPE. This is largely attributed to the large amount of crystalline spherulites present in the HDPE material, which scatter the light.
  • the optics-enhancing additives may include one or more monomeric and/or polymeric additives that are partially and/or fully dispersible within the HDPE.
  • additives will hereinafter be referred to as “dispersible additives,” “dispersible monomeric and/or polymeric additives,” “dispersible monomeric additives,” “dispersible polymeric additives” or similar expressions unless it is otherwise stated or is apparent from the context.
  • Such “dispersible additives” include those that are both partially dispersible and fully dispersible within the HDPE materials. These dispersible additives may be used in combination with a further optics enhancing additive of a clarifying and/or nucleating agent.
  • additives is believed to reduce the size and/or modify the shape of the crystalline spherulites in the HDPE composition when the melt blend begins to crystallize, such as during the molding of the HDPE article, thereby leading to the lowering of percentage crystallinity and/or the lowering of size of crystalline spherulites and/or the alteration of the shape of crystalline spherulites. This is true even though the additives are added during melt mixing of the HDPE during the extrusion process.
  • optics-enhancing additives may be selected and used in amounts so that the processability, flow properties, and mechanical properties remain mainly unaffected, while the optical properties are improved. This is important because in addition to the optic-enhancing additives reducing the size and/or altering the shape of the crystalline spherulites, the optic enhancing additives may also lower the overall percentage crystallinity of the HDPE composition by 30% to 80% of its original value without the use of the optics-enhancing additives.
  • the optic-enhancing additives may lower the overall percentage crystallinity of the HDPE composition by at least equal to, and/or between any two of 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%,
  • the optics-enhancing dispersible additive is one that is either partially soluble or partially miscible with the HDPE material under the processing conditions used in forming the HDPE composition or one that is fully soluble or fully miscible with the HDPE material under the processing conditions used in forming the HDPE composition.
  • the terms “soluble” or “miscible” and variations of these terms may be used interchangeably unless otherwise apparent from its context. Partial solubility or partial miscibility refers to those materials that do not form distinct domain morphology, but rather form a co-continuous morphology or no distinction can be made in transmission electron microscopy (TEM) and/or scanning electron microscopy (SEM) analyses.
  • TEM transmission electron microscopy
  • SEM scanning electron microscopy
  • the dispersible additives which may be any one or a combination of two or more different monomeric and/or polymeric additives that are partially and/or fully dispersible within the HDPE, may be used in an amount of from 0.1 wt.% to 5 wt.% by total weight of the HDPE composition.
  • the total amount of the dispersible additives used may be at least, equal to, and/or between any two of 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt.%, 1.1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 1.7 wt.%, 1.8 wt.%, 1.9 wt.%, 2.0 wt.%, 2.1 wt.%, 2.2 wt.%, 2.3 wt.%, 2.4 wt.%, 2.5 wt.%, 2.6 wt.%, 2.7 wt.%, 2.8 wt.%, 2.9
  • Non-limiting examples of suitable partially or fully dispersible monomers for use as the optic-enhancing additive include monomeric long-alkyl-chain-containing phase change materials such as methyl laurate, 1 -decanol, and tetradecane. Such dispersible monomers get dispersed within the HDPE matrix and interfere or co-crystallize with the crystallization of the HDPE component during solidification of the polymer melt.
  • Non-limiting examples of suitable partially or fully dispersible polymers for use as the optic-enhancing additive include low density polyethylenes (LDPE), linear low density polyethylenes (LLDPE), branched polyethylenes, low molecular weight high density polyethylenes, ultrahigh molecular weight polyethylenes (UHMWPE), polyolefin elastomers (POE), polyolefin plastomers (POP), and maleic anhydride grafted polyethylenes. Most of these polymers contain ethylene blocks that facilitate their dispersibility or miscibility with the HDPE component.
  • LDPE low density polyethylenes
  • LLDPE linear low density polyethylenes
  • UHMWPE ultrahigh molecular weight polyethylenes
  • POE polyolefin elastomers
  • POP polyolefin plastomers
  • maleic anhydride grafted polyethylenes Most of these polymers contain ethylene blocks that facilitate their dispersibility or miscibility with the HDPE component.
  • the LDPE used as the dispersible polymeric additive may be that have a density ranging from 0.910 kg/m 3 to 0.925 kg/m 3 as per ASTM D1505.
  • the LDPE may have melt flow rate of from 10 g/10 min to 40 g/10 min at 190°C and with 2.16 Kg load.
  • the LDPE may have a melt flow rate of from at least, equal to, and/or between any two melt flow rate of 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min, 36 g/10 min, 37 g/10 min, 38 g/10 min, 39 g/10 min, and 40 g/10 min at 190°C and with 2.16 Kg load.
  • the LLDPE used as the dispersible polymeric additive may be that have a density ranging from 0.910 kg/m 3 to 0.940 kg/m 3 as per ASTM D1505.
  • the LLDPE may have melt flow rate of from 1 g/10 min to 40 g / 10 min at 190°C and with 2.16 Kg load.
  • the LLDPE may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min, 36 g/10 min, 37 g/10 min, 30
  • the branched polyethylene used as the dispersible polymeric additive may be LDPE or HDPE that have a density ranging from 0.90 kg/m 3 to 0.97 kg/m 3 as per ASTM D1505.
  • the branched polyethylene may have melt flow rate of from 0.1 g/ 10 min to 40 g / 10 min at 190°C and with 2.16 Kg load.
  • the branched polyethylene may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min,
  • the low molecular weight high density polyethylene used as the dispersible polymeric additive may be that having a density of from 940 kg/m 3 or 945 kg/m 3 to 965 kg/m 3 as per ASTM D1505.
  • the low molecular weight high density polyethylene may have melt flow rate of from 1 g/ 10 min to 40 g / 10 min at 190°C and with 2.16 Kg load.
  • the low molecular weight high density polyethylene may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min, 36 g/10 min, 10
  • the ultrahigh molecular weight polyethylene (UHMWPE) used as the dispersible polymeric additive may be that having a density of from 930 kg/m 3 to 950 kg/m 3 as per ASTM D1505.
  • the UHMWPE may have melt flow rate of from 0.1 g/ 10 min to 5 g/ 10 min at 190°C and with 21.6 Kg load.
  • the UHMWPE may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1.0 g/10 min, 1.1 g/10 min, 1.2 g/10 min, 1.3 g/10 min, 1.4 g/10 min, 1.5 g/10 min, 1.6 g/10 min, 1.7 g/10 min, 1.8 g/10 min, 1.9 g/10 min, 2.0 g/10 min, 2.1 g/10 min, 2.2 g/10 min, 2.3 g/10 min, 2.4 g/10 min, 2.5 g/10 min, 2.6 g/10 min, 2.7 g/10 min,
  • the polyolefin elastomer (POE) used as the dispersible polymeric additive may be that having a density of from 840 kg/m 3 to 930 kg/m 3 as per ASTM D1505.
  • the POE may have melt flow rate of from 0.1 40 g/ 10 min to 40 g / 10 min at 190°C and with 2.16 Kg load.
  • the POE may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g
  • the polyolefin plastomer (POP) used as the dispersible polymeric additive may be that having a density of from 850 kg/m 3 to 920 kg/m 3 as per ASTM D1505.
  • the POP may have melt flow rate of from 0.1 g/ 10 min to 40 g / 10 min at 190°C and with 2.16 Kg load.
  • the POP may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g
  • the maleic anhydride grafted polyethylene used as the dispersible polymeric additive may be that having a density ranging from 0.910 kg/m 3 to 0.960 kg/m 3 as per ASTM D1505.
  • the maleic anhydride grafted polyethylene may have melt flow rate of from 1 g/ 10 min to 40 g/ 10 min at 190°C and with 2.16 Kg load.
  • the maleic anhydride grafted polyethylene may have a melt flow rate of from at least, equal to, and/or between any two melt flow rate of 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min, 36 g/10 min,
  • the optics-enhancing additive of a clarifying and/or nucleating agent may be used in combination with dispersible additives discussed above.
  • Nucleating agents may be considered as those additives that are added to polymers to facilitate crystal growth in the polymer melt. Those nucleating agents that can be classified as clarifying agents also facilitate crystal growth, but the crystal growth is reduced in comparison to nucleating agents that can be classified as non-clarifying nucleating agents, leading to a reduction in the size and shape of the crystalline spherulite of semi-crystalline polymers.
  • the term “clarifying agent” and similar expressions are meant to encompass those nucleating agent compounds that facilitate crystal growth where the crystal growth results in a reduced crystalline spherulite size from those that would result without the clarifying agent.
  • nucleating agent and similar expressions are used, unless otherwise specified, it is meant to include those compounds that form nuclei for facilitating crystal growth in the polymer melt with or without reducing the size of the crystalline spherulites. Such nucleating agents would broadly cover clarifying agents, as well.
  • non-clarifying nucleating agent and similar expressions is meant to encompass those nucleating agents that do not normally reduce the size of the crystalline spherulites or that would not be classified as a clarifying agent.
  • clarifying and/or nucleating agents have been commonly used with such materials as polypropylene (PP), polyethylene terephthalate (PET), nylon, etc., they have not been used commercially with polyethylene. This is because polyethylene has a very high crystallization rate and kinetics. The rate of crystallization is difficult to control compared to other polymers. Furthermore, HDPE has a relatively high percentage crystallinity compared to these other polymers, such that the use of nucleating agents is not necessary.
  • the clarifying and/or nucleating agents When used in specific amounts in forming the HDPE compositions described herein, the clarifying and/or nucleating agents have been shown to increase the transparency and/or reduce haze in the HDPE compositions without significantly affecting the crystallinity of the HDPE composition to a degree that the desired flow characteristics, processability, and mechanical properties are significantly altered. This is particularly true when used in combination with the dispersible additives, as discussed previously, where they may have a synergistic effect.
  • the amount of the clarifying and/or nucleating agents may range from 50 ppm to 500 ppm by total weight of the HDPE composition.
  • the clarifying and/or nucleating agent may be used in an amount of from at least, equal to, and/or between any two of 50 ppm, 51 ppm, 52 ppm, 53 ppm, 54 ppm, 55 ppm, 56 ppm, 57 ppm, 58 ppm, 59 ppm, 60 ppm, 61 ppm, 62 ppm, 63 ppm, 64 ppm, 65 ppm, 66 ppm, 67 ppm, 68 ppm, 69 ppm, 70 ppm, 71 ppm, 72 ppm, 73 ppm, 74 ppm, 75 ppm, 76 ppm, 77 ppm, 78 ppm, 79 ppm, 80 ppm, 81 ppm, 82 ppm, 83 ppm, 84 ppm, 85 ppm, 86 ppm, 87 ppm, 88 ppm,
  • Non-limiting examples of suitable nucleating agents include calcium salts of dicarboxylic acid, metal salts of cyclohexane dicarboxylic acid, bisamide, lithium carbonate, benzoic acid, inorganic oxides, nano- zinc oxides, talc, clay, powdered polymeric agents such as polyphenylene oxide, polyvinylenedifluoride, polycarbonate, polycarbonate-siloxane copolymer, cross-linked polycarbonate, polyetherimide, polyamide, ethylene propylene diene monomer, and polyoxymethylene.
  • a non-limiting example of a suitable commercially available nucleating agent is that available as HYPERFORMTM HPN-20E, available from Milliken & Company, which is a calcium salt of cyclohexane dicarboxylic acid.
  • Non-limiting examples of suitable clarifying agents include sorbitol derivatives,
  • DBS 1.2.3.4-bis-dibenzylidene sorbitol
  • DOS l,2,3,4-bis-(p-methoxybenzylidene sorbitol)
  • MBDS 1.2.3.4-bis-(3,4-dimethylbenzylidene sorbitol)
  • DDBS l,3:2,4-di(3,4- dimethylbenzylidene) sorbitol
  • the polyethylene compositions can further include at least one additional optional or secondary additive, as distinguished from the optics-enhancing dispersible additives and clarifying and/or nucleating agents discussed above.
  • additional optional or secondary additives may be those that do not necessarily impact or increase the transparency or haze of the final product.
  • Non-limiting examples of additional optional or secondary additives include a heat conductive agent, a tie agent, an antiblocking agent, an antistatic agent, an antioxidant, a neutralizing agent, an acid scavenger, a blowing agent, a dye, a flame retardant agent, a filler (hard or soft), an impact modifier, a mold release agent, an oil, another polymer, a pigment, a processing agent, a reinforcing agent, a stabilizer (including light stabilizers), an UV resistance agent, a slip agent, a flow modifying agent, and combinations thereof.
  • a heat conductive additive is present in the polymer blend in an amount of at least, equal to, and/or between any two of 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 1.0 wt. % by total weight of the polymer blend.
  • Non-limiting examples of heat conductive additive include, aluminum oxide, titanium dioxide, graphitic compounds, graphenes, boron nitride, aluminum nitride, zinc oxide [0056]
  • a tie molecule is present in the polymer blend in amount of at least, equal to, and/or between any two of 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 1.0 wt. % by total weight of the polymer blend.
  • Non- limiting examples of tie molecules include, linear low-density polyethylene, low-density polyethylene, and medium density polyethylene.
  • a filler is present in the polymer blend in amount of at least, equal to, and/or between any two of 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt. %, 2.0 wt. %, 3.0 wt. %, 4.0 wt. %, 5.0 wt. %, 6.0 wt. %, 7.0 wt. %, 8.0 wt. %, 9.0 wt.
  • the filler can be a hard filler.
  • hard filler include, inorganic particulate fillers such as silica, calcium carbonate, inorganic layered fillers such as clays, mica.
  • the filler can be a soft filler.
  • soft filler include, immiscible particulate elastomeric/polymeric resins.
  • the filler can also be a hollow filler.
  • Non limiting examples of hollow filler include, glass microspheres, plastic microspheres, ceramic microspheres such as cenospheres made up of alumino silicate microspheres, metallic microspheres made up of aluminum and copper/silver microspheres, and phenolic microspheres.
  • a light stabilizer is present in the polymer blend in an amount of at least, equal to, and/or between any two of 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 1.0 wt. % by total weight of the polymer blend.
  • the light stabilizer can be a hindered amine light stabilizer.
  • hindered amine light stabilizer refers to a class of amine compounds having certain light stabilizing properties.
  • HALS hindered amine light stabilizers
  • HALS include 1-cyclohexyloxy- 2,2,6,6-tetramethyl-4-octadecylaminopiperidine; bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(l-acetoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(l,2,2,6,6- pentamethylpiperidin-4-yl) sebacate; bis(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(l-acyl-2, 2,6,6- tetramethylpiperidin-4-yl) sebacate; bis(l,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-d
  • N-H sterically hindered N-H, N-methyl, N-methoxy, N-hydroxy, N-propoxy, N-octyloxy, N-cyclohexyloxy, N-acyloxy and N-(2-hydroxy-2-methylpropoxy) analogues of any of the above-mentioned compounds.
  • Non limiting examples of commercial light stabilizer are available from BASF under the trade name Uvinul® 4050H, 4077H, 4092H, 5062H, 5050H, 4092H, 4077H, 3026, 3027, 3028, 3029, 3033P, and 3034 or Tinuvin® 622.
  • Anti-static agents can be used to inhibit accumulation of dust on plastic articles. Antistatic agents can improve the electrical conductivity of the plastic compositions, and thus dissipate any surface charges, which develop during production and use. Thus, dust particles are less attracted to the surface of the plastic article, and dust accumulation is consequently reduced.
  • the antistatic agent can be a glycerol monostearate.
  • the polymer blend can include an anti-static agent in an amount of at least, equal to, and/or between any two 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 1 wt. % by total weight of the polymer blend.
  • a lubricant can be added to a polymer blend to improve the mold-making characteristics.
  • the lubricant can be a low molecular compound from a group of fatty acids, fatty acid esters, wax ester, fatty alcohol ester, amide waxes, metal carboxylate, montanic acids, montanic acid ester, or such high molecular compounds, as paraffins or polyethylene waxes.
  • the lubricant is a metal stearate.
  • metal stearates include zinc stearate, calcium stearate, lithium stearate or a combination thereof, preferably calcium stearate.
  • the polymer blend can include a lubricant in an amount of at least, equal to, and/or between any two of 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 1 wt. % by total weight of the polymer blend.
  • An antioxidant can provide protection against polymer degradation during processing.
  • Phosphites are known thermal oxidative stabilizing agents for polymers and other organic materials.
  • the antioxidant can be a phosphite-based antioxidant.
  • phosphite- antioxidants include, but are not limited to, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite tristearyl
  • the polymer blend can include an antioxidant in an amount of at least, equal to, and/or between any two of 0.01 wt.%, 02 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 0.1 wt. % by total weight of the polymer blend.
  • Non-limiting examples of commercially available antioxidants include Irganox 1010 available from BASF, or Doverphos S9228T available from Dover Chemical Company.
  • the various components of the HDPE, the optics enhancing dispersible additive and clarifying and/or nucleating agent, as described, along with any additional optional additives can be dry blended.
  • the HDPE component may be in the form of pellets, powder, flakes or fluff.
  • the materials are combined in a customary mixing machine, in which the HDPE, optics-enhancing additives, and nucleating agents are mixed with any optional additional or secondary additives.
  • the optional additional additives can be added at the end or during the processing steps to produce the polymer blend. Suitable machines for such mixing are known to those skilled in the art. Non-limiting examples include mixers, kneaders and extruders.
  • extruders are then fed directly into the feed zone of an extruder.
  • the process can be carried out in an extruder and introduction of the additives may occur during processing.
  • suitable extruders include single screw extruders, counter-rotating and co-rotating twin-screw extruders, planetary-gear extruders, ring extruders, or co-kneaders.
  • the process can be performed at a temperature from 160 °C to 300 °C.
  • the HDPE, optics-enhancing additives of the dispersible additive and clarifying and/or nucleating agents, and any optional secondary additives, used to produce the polymer blend of the present invention can be melt-extruded by following typical procedures of weighing the required amounts of the HDPE and additives, followed by dry blending, and then feeding the mixture into a main feeder of a twin-screw co-rotating extruder (length/diameter (L/D) ratio of 25:1 or 40:1) to obtain the final composition.
  • the HDPE, additives, or blend thereof can be subjected to an elevated temperature for a sufficient period of time during blending.
  • the blending temperature can be above the softening point of the polymers.
  • the extrusion process can be performed at a temperature from 160 °C to 300 °C.
  • the optics-enhancing dispersible additives and clarifying and/or nucleating agents can be added along with other optional additives in-line and prior to pelletization of the HDPE resin during the production process.
  • the amounts of additives combined with the HDPE can be adjusted to provide those weight amounts previously discussed.
  • the optional secondary additives can be premixed or added individually to the polymer blend or the different components thereof.
  • the secondary additives of the present invention can be premixed such that the blend is formed prior to adding it to the HDPE or the optics-enhancing additives.
  • the blend thereof can be subjected to an elevated temperature for a sufficient period of time during blending and/or incorporation of additives.
  • Incorporation of optional secondary additives into the polymer resin can be carried out, for example, by mixing the above-described components using methods customary in process technology.
  • the blending temperature can be above the softening point of the polymers.
  • a process can be performed at a temperature from 160 °C to 300 °C. Such “melt mixing” or “melt compounding” results in uniform dispersion of the present optional additives in the HDPE and/or optic-enhancing additives.
  • Articles e.g., caps, bottles and containers
  • the blend of HDPE and optics-enhancing additives can have a higher transparency and/or reduced haze than articles of manufacture made from HDPE without such additives.
  • the HDPE composition may have a transparency of from 80% or more and a haze of from 60% or less as determined by ASTM D1003 at a thickness of from 1 mm or more, with or without any drawing, stretching or orienting of the HDPE composition.
  • the HDPE composition may have a transparency of at least, equal to, and/or between any two of 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%,
  • the haze of the HDPE composition may be from at least equal to, and/or between any two of 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 29%, 30%, 31%, 32%, 33%, 34%, 35%,
  • the transparency of the HDPE composition may provide an article with a transparency of from 90% or more and a haze of from 50% or less as determined by ASTM D1003 at a thickness of from 1 mm or more, with or without any drawing, stretching or orienting the HDPE composition.
  • the polymer blend compositions formed as described are normally collected as pellets, which can be stored for a time or employed immediately in a forming process.
  • the forming processes can include injection molding, blow molding, compression molding, sheet extrusion, film blowing, pipe extrusion, profile extrusion, calendaring, thermoforming, rotomolding, or combinations thereof.
  • the final formed articles can be, for instance, molded parts, sheets, films, or fibers. Examples of molded parts include a cap, a bottle cap, a container, a bottle, a lid, a sheet, a pipe, a pipe coupling, a bottle, a cup, a tray, a pallet, or a toy, or combinations thereof.
  • Caps can be injection and/or compression molded.
  • the caps may be threaded or non- threaded caps for selectively closing off openings to bottles or other containers. Such caps can be used in a variety of food and non-food applications.
  • caps and containers that include the polymer blend of the present invention can be used with containers for storing carbonated beverages, pressurized beverages, or the like.
  • Different optics-enhancing additives comprising an optic-enhancing partially soluble or fully soluble monomeric and/or polymeric additive in combination with clarifying and/or nucleating agents for increasing the transparency and/or reducing haze in HDPE.
  • the HDPE compositions were prepared using SABIC ® HDPE B5823, which is a unimodal HDPE having an MFR at 190° C and 5 kg of 0.9 g/ 10 min and a density of 958 kg/m 3 .
  • Different optics enhancing additives for increasing the transparency and/or reducing haze in HDPE were used with the B5823 HDPE.

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Abstract

A high-density polyethylene (HDPE) composition has increased transparency and/or reduced haze. The composition is a mixture of a HDPE, a monomeric and/or polymeric additive that is partially and/or fully dispersed within the HDPE, and a clarifying and/or nucleating agent in an amount of 50 ppm to 500 ppm by total weight of the HDPE composition. The HDPE composition has at least one of a transparency of from 80% or more and a haze of from 60% or less as determined by ASTM D1003 at a thickness of from 1 mm or more.

Description

HIGH-DENSITY POLYETHYLENE WITH ADDITIVES FOR INCREASED
TRANSPARENCY
TECHNICAL FIELD
[0001] The invention relates to high-density polyethylene compositions that have improved transparency and/or reduced haze.
BACKGROUND
[0002] Though high-density polyethylene (HDPE) has been widely used to fabricate rigid parts and objects, including small and large containers and caps and closures owing its excellent mechanical and environmental stress cracking resistance (ESCR) performances, its use in transparent applications is limited. This is due to its inherently opaque or translucent appearance. Though one can potentially improve the transparency (or reduce the total haze) via several post-processing steps, such as stretching or drawing to a different extent, both with and without additives, such methods are not commercially or economically viable. As a result, there is a need to improve the transparency of HDPE compositions towards expanding their applications into transparent segments.
SUMMARY
[0003] A high-density polyethylene (HDPE) composition having increased transparency and/or reduced haze comprises a mixture of a HDPE, a monomeric and/or polymeric additive that is partially and/or fully dispersed within the HDPE, and a clarifying and/or nucleating agent in an amount of 50 ppm to 500 ppm by total weight of the HDPE composition. The HDPE composition has at least one of a transparency of from 80% or more and a haze of from 60% or less as determined by ASTM D1003 at a thickness of from 1 mm or more.
[0004] The HDPE composition may have at least one of a transparency of from 90% or more and a haze of from 50% or less as determined by ASTM D1003 at a thickness of from 1 mm or more, without drawing, stretching or orienting the HDPE composition.
[0005] The HDPE may be at least one of a unimodal, bimodal, and multimodal HDPE. In particular embodiments, the HDPE may have an average molecular weight (Mw) of from 130,000 to 300,000 as determined by high temperature gel permeation chromatography; a poly dispersity index (PDI = Mw/Mn) of from 2 to 25 as determined by high temperature gel permeation chromatography; a melt flow rate (MFR) at 190 °C and 5 kg of from 0.1 g/10 min to 20 g/10 min as per ISO 1133; and/or a density of from 940 kg/m3 to 965 kg/m3 as per ASTM D1505.
[0006] The monomeric and/or polymeric additive may be present in an amount of from 0.1 wt.% to 5 wt.% by total weight of the HDPE composition. The monomeric and/or polymeric additive is selected from at least one of a monomeric phase change material, methyl laurate, 1-decanol and tetradecane, a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a branched polyethylene, a low molecular weight high density polyethylene, an ultrahigh molecular weight polyethylene (UHMWPE), a polyolefin elastomer (POE), a polyolefin plastomer (POP), maleic anhydride grafted polyethylene, and combinations thereof.
[0007] The clarifying and/or nucleating agent may be present in an amount of 100 ppm to 200 ppm by total weight of the HDPE composition. The clarifying and/or nucleating agent may be selected from at least one of a sorbitol derivative, 1,2,3,4-bis-dibenzylidene sorbitol (DBS), l,2,3,4-bis-(p-methoxybenzylidene sorbitol) (DOS), l,2,3,4-bis-(3,4-dimethylbenzylidene sorbitol) (MBDS), and l,3:2,4-di(3,4-dimethylbenzylidene) sorbitol (DMDBS), a calcium salt of dicarboxylic acid, a metal salt of cyclohexane dicarboxylic acid, a bisamide, a lithium carbonate, a benzoic acid, an inorganic oxide, nano-zinc oxide, talc, clay, a powdered polymeric agent, polyphenylene oxide, polyvinylenedifluoride, polycarbonate, polycarbonate- siloxane copolymer, cross-linked polycarbonate, polyetherimide, polyamide, ethylene propylene diene monomer, and polyoxymethylene.
[0008] The HDPE may be a copolymer with comonomers selected from C3 to C10 olefin monomers, the comonomers being present in the HDPE copolymer in an amount of from 2 wt.% or less.
[0009] In certain applications, the HDPE composition may further include one or more of a heat conductive agent, a tie agent, an antiblocking agent, an antistatic agent, an antioxidant, a neutralizing agent, an acid scavenger, a blowing agent, a crystallization aid, a dye, a flame retardant agent, a filler, a hard filler, a soft filler, an impact modifier, a mold release agent, an oil, another polymer, a pigment, a processing agent, a reinforcing agent, a stabilizer, a light stabilizer, an UV resistance agent, a slip agent, a flow modifying agent, and combinations thereof.
[0010] The HDPE composition may be formed into an article of manufacture. The article may be one or more of a film, a molded part, a container, a beverage container cap, a lid, a sheet, a pipe, a pipe coupling, a bottle, a cup, a tray, a pallet, and a toy. The article may be formed by injection molding, blow molding, compression molding, sheet extrusion, film blowing, pipe extrusion, profile extrusion, calendaring, or thermoforming.
[0011] In more specific embodiments, a high-density polyethylene (HDPE) composition having increased transparency and/or reduced haze comprises a mixture of a HDPE, a monomeric and/or polymeric additive that is partially and/or fully dispersed within the HDPE in an amount of from 0.1 wt.% to 5 wt.% by total weight of the HDPE composition. The HDPE composition further includes a clarifying and/or nucleating agent in an amount of 100 ppm to 500 ppm by total weight of the HDPE composition. The HDPE composition has a transparency of from 80% or more and/or a haze of from 40% or less as determined by ASTM D1003 at a thickness of from 1 mm or more, without drawing, stretching or orienting the HDPE composition.
[0012] The monomeric and/or polymeric additive is selected from at least one of a monomeric phase change material, methyl laurate, 1-decanol and tetradecane, a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a branched polyethylene, a low molecular weight high density polyethylene, an ultrahigh molecular weight polyethylene (UHMWPE), a poly olefin elastomer (POE), a poly olefin plastomer (POP), maleic anhydride grafted polyethylene, and combinations thereof.
[0013] The clarifying and/or nucleating agent is selected from at least one of a sorbitol derivative, 1,2,3,4-bis-dibenzylidene sorbitol (DBS), l,2,3,4-bis-(p-methoxybenzylidene sorbitol) (DOS), l,2,3,4-bis-(3,4-dimethylbenzylidene sorbitol) (MBDS), and l,3:2,4-di(3,4- dimethylbenzylidene) sorbitol (DMDBS), a calcium salt of dicarboxylic acid, a metal salt of cyclohexane dicarboxylic acid, a bisamide, a lithium carbonate, a benzoic acid, an inorganic oxide, nano-zinc oxide, talc, clay, powdered polymeric agents such as polyphenylene oxide, polyvinylenedifluoride, polycarbonate, polycarbonate- siloxane copolymer, cross-linked polycarbonate, polyetherimide, polyamide, ethylene propylene diene monomer, and polyoxymethylene.
[0014] In certain instances, the clarifying and/or nucleating agent is present in an amount of 100 ppm to 200 ppm by total weight of the HDPE composition.
[0015] The HDPE may be at least one of a unimodal, bimodal, and multimodal HDPE. In particular cases, the HDPE may have an average molecular weight (Mw) of from 130,000 to 300,000 as determined by high temperature gel permeation chromatography; a poly dispersity index (PDI = Mw/Mn) of from 10 to 25 as determined by high temperature gel permeation chromatography; a melt flow rate (MFR) at 190 °C and 5 kg of from 0.5 g/10 min to 5 g/10 min as per ISO 1133; and/or a density of from 940 kg/m3 to 965 kg/m3 as per ASTM D1505. The polymer blend may be formed into an article of manufacture. The article may be a film, a molded part, a container, a bottle, a beverage container cap, a lid, a sheet, a pipe, a pipe coupling, a bottle, a cup, a tray, a pallet, and a toy.
[0016] In a method of forming a high-density polyethylene (HDPE) composition having increased transparency and/or reduced haze, a HDPE is modified by combining the HDPE with a monomeric and/or polymeric additive that is partially and/or fully dispersed within the HDPE, and a clarifying and/or nucleating agent in an amount of 100 ppm to 500 ppm by total weight of the HDPE composition so that the HDPE composition has at least one of a transparency of from 80% or more and a haze of from 60% or less as determined by ASTM D1003 at a thickness of from 1 mm or more.
DETAILED DESCRIPTION
[0017] The present invention is related to the development of high-density polyethylene (HDPE) compositions, which may be used in various applications, such as blow/injection/compression moldable applications, with improved transparency. This includes several packaging applications, including caps and closures, trays, pipes, toys, chemical containers, shampoo bottles, milk jugs, recycling bins, and industrial bulk containers. Given the growing demand for aesthetics and see-through features of plastic parts (for example, caps and closure, bottles and containers), an enhanced optically transparent plastic becomes more vital. Bottles that are less opaque than those traditionally used have been placed on the market recently. The use of bottles having greater clarity can be aesthetically appealing to consumers. Such greater clarity allows the consumer to see the consistency of the product, any suspended particles if they are present, separation of phases if a dual phase composition is present, and other aspects or properties of materials contained in such bottles, such as laundry liquid products. Transparent bottles may also be appealing to consumers during use as it enables the consumer to ascertain easily how much product remains. The reduction of total haze of molded parts, as demanded by the consumers, while maintaining the inherent mechanical strength and processability of the HDPE is an emerging challenge. In comparison to transparent glass, the transparent HDPE composition is envisaged to have light weight and higher impact resistance. Moreover, the transparent HDPE composition is envisaged to have better hydrolytic stability and moisture barrier resistance, as compared to transparent polymers such as polycarbonate and polymethylmethacrylate.
[0018] It has been discovered that the transparency of HDPE can be increased by incorporating various optics-enhancing additives. Additionally, the total haze of the HDPE can be reduced by the use of such optics-enhancing additives. These optics-enhancing additives are incorporated into a unimodal, bimodal or multimodal HDPE, or a blend of these, by melt blending the optics-enhancing additives with the HDPE. The amount and the type of the optics enhancing additives incorporated into the HDPE is selected so that the processability of the HDPE remains relatively unaffected while its transparency and/or reduction in haze is enhanced.
[0019] The HDPE polymers used in the polymer blend can include those prepared by any of the polymerization processes, which are in commercial use (e.g., a “high pressure” process, a slurry process, a solution process and/or a gas phase process) and with the use of any of the known catalysts (e.g., multisite catalysts such as Ziegler Natta catalysts, and/or single site catalysts such as chromium or Phillips catalysts, metallocene catalysts, and the like). As used herein, where the phrase or term “high-density polyethylene” or “HDPE” is used, it should be construed without characterization as unimodal, bimodal or multimodal HDPE unless otherwise specified.
[0020] All or a major portion of the HDPE component may be unimodal or bimodal HDPE, either alone or as a blend. The unimodal and/or hi modal HDPE or combination of such HDPE materials may make up from 50 wt.% or greater of the HDPE component or from 50 wt.% to 100 wt.% of the HDPE component. In particular embodiments, the HDPE component may comprise unimodal and/or hi modal HDPE in an amount of from at least, equal to, and/or between any two of 50 wt.%, 51 wt.%, 52 wt.%, 53 wt.%, 54 wt.%, 55 wt.%, 56 wt.%, 57 wt.%, 58 wt.%, 59 wt.%, 60 wt.%, 61 wt.%, 62 wt.%, 63 wt.%, 64 wt.%, 65 wt.%, 66 wt.%, 67 wt.%, 68 wt.%, 69 wt.%, 70 wt.%, 71 wt.%, 72 wt.%, 73 wt.%, 74 wt.%, 75 wt.%, 76 wt.%,
77 wt.%, 78 wt.%, 79 wt.%, 80 wt.%, 81 wt.%, 82 wt.%, 83 wt.%, 84 wt.%, 85 wt.%, 86 wt.%,
87 wt.%, 88 wt.%, 89 wt.%, 90 wt.%, 91 wt.%, 92 wt.%, 93 wt.%, 94 wt.%, 95 wt.%, 96 wt.%,
97 wt.%, 98 wt.%, 99 wt.%, and 100 wt.%. In particular embodiments, the HDPE component may comprise unimodal and/or hi modal HDPE in an amount of from 80 wt.% to 100 wt.%. If less than 100 wt.% of unimodal and/or hi modal HDPE is used for the HDPE component, the remainder may be made up of multimodal HDPE. In certain aspects, the polymer blends of the present invention do not include polypropylene.
[0021] In other embodiments, all or a major portion of the HDPE component may be multimodal HDPE. The multimodal HDPE may make up from 50 wt.% or greater of the HDPE component or from 50 wt.% to 100 wt.% of the HDPE component. In particular embodiments, the HDPE component may comprise multimodal HDPE in an amount of from at least, equal to, and/or between any two of 50 wt.%, 51 wt.%, 52 wt.%, 53 wt.%, 54 wt.%, 55 wt.%, 56 wt.%, 57 wt.%, 58 wt.%, 59 wt.%, 60 wt.%, 61 wt.%, 62 wt.%, 63 wt.%, 64 wt.%, 65 wt.%, 66 wt.%, 67 wt.%, 68 wt.%, 69 wt.%, 70 wt.%, 71 wt.%, 72 wt.%, 73 wt.%, 74 wt.%, 75 wt.%,
76 wt.%, 77 wt.%, 78 wt.%, 79 wt.%, 80 wt.%, 81 wt.%, 82 wt.%, 83 wt.%, 84 wt.%, 85 wt.%,
86 wt.%, 87 wt.%, 88 wt.%, 89 wt.%, 90 wt.%, 91 wt.%, 92 wt.%, 93 wt.%, 94 wt.%, 95 wt.%,
96 wt.%, 97 wt.%, 98 wt.%, 99 wt.%, and 100 wt.%. In particular embodiments, the HDPE component may comprise multimodal HDPE in an amount of from 80 wt.% to 100 wt.%. If less than 100 wt.% of multimodal HDPE is used for the HDPE component, the remainder may be made up of unimodal and/or bimodal HDPE. If less than 100 wt.% of unimodal and/or hi modal HDPE is used for the HDPE component, the remainder may be made up of multimodal HDPE. In certain aspects, the polymer blends of the present invention do not include polypropylene.
[0022] It should be noted in the description, if a numerical value, concentration or range is presented, each numerical value should be read once as modified by the term "about" (unless already expressly so modified), and then read again as not so modified unless otherwise indicated in context. Also, in the description, it should be understood that an amount range listed or described as being useful, suitable, or the like, is intended that any and every value within the range, including the end points, is to be considered as having been stated. For example, “a range of from 1 to 10” is to be read as indicating each and every possible number along the continuum between about 1 and about 10. Thus, even if specific points within the range, or even no point within the range, are explicitly identified or referred to, it is to be understood that the inventor appreciates and understands that any and all points within the range are to be considered to have been specified, and that inventor possesses the entire range and all points within the range, including smaller ranges within the larger ranges.
[0023] In certain applications, the HDPE component of the polymer blend will constitute homopolymers of ethylene. These may include homopolymers solely of neat HDPE. In other embodiments, the HDPE component can include copolymers of ethylene with at least one C3 to C10 alpha olefin. Typically, this will be at least one of the alpha olefins of butene, hexene, and/or octene. In some embodiments the HDPE is a copolymer with 1 -butene (polyethylene- 1 -butene) or 1 -hexene (polyethylene- 1 -hexene). When such copolymers are used, the non ethylene comonomer may be present in the HDPE copolymer in an amount of from 2 wt.%, 1.5 wt.%, 1 wt.%, 0.5 wt.%, 0.1 wt.% or less. In particular embodiments, there is no butene or no C3 to C10 alpha olefin comonomer. Those amount percentages of multimodal HDPE, hi modal HDPE, and/or unimodal HDPE presented previously for the HDPE component may include such HDPE incorporating such copolymers.
[0024] In certain embodiments, the main HDPE component may be an un-functionalized neat HDPE with no functional groups along the polymer chain. In particular embodiments, the HDPE contains anhydride modified HDPE as an additive which is present in an amount of from 2 wt.%, 1.5 wt.%, 1 wt.%, 0.5 wt.%, 0.1 wt.% or less.
[0025] The HDPE can be characterized by various properties such as average molecular weight, poly dispersity index, density, the melt flow rates (MFR), ESCR, tensile strength at yield, tensile modulus, tensile elongation at yield, Izod notched impact strength, hardness or combinations thereof. [0026] The average molecular weight (Mw) of the HD PE may range from 130,000 to 300,000 as determined by high temperature gel permeation chromatography. In particular, the average molecular weight (Mw) of the HDPE may be from at least, equal to, and/or between any two of 130,000, 140,000, 150,000, 160,000, 170,000, 180,000, 190,000, 200,000, 210,000, 220,000, 230,000, 240,000, 250,000, 260,000, 270,000, 280,000, 290,000, and 300,000 as determined by high temperature gel permeation chromatography. Unless otherwise specified, all average molecular weights (Mw) for those polymers described herein are those determined by high temperature gel permeation chromatography.
[0027] The density of the HDPE can be from 940 kg/m3 or 945 kg/m3 to 965 kg/m3. In particular, the density of the HDPE may be from at least, equal to, and/or between any two of
940 kg/m3, 941 kg/m3, 942 kg/m3, 943 kg/m3, 944 kg/m3, 945 kg/m3, 946 kg/m3, 947 kg/m3,
948 kg/m3, 949 kg/m3, 950 kg/m3, 951 kg/m3, 952 kg/m3, 953 kg/m3, 954 kg/m3, 955 kg/m3,
956 kg/m3, 957 kg/m3, 958 kg/m3, 959 kg/m3, 960 kg/m3, 961 kg/m3, 962 kg/m3, 963 kg/m3,
964 kg/m3, and 965 kg/m3. In some applications, the density of the HDPE may range from 955 kg/m3 to 965 kg/m3.
[0028] The HDPE can have a MFR at 190 °C and 5 kg of from 0.1 g/10 min to 20 g/10 min as per ISO 1133, or at least, equal to, and/or between any two of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1.0 g/10 min, 1.1 g/10 min, 1.2 g/10 min, 1.3 g/10 min, 1.4 g/10 min, 1.5 g/10 min, 1.6 g/10 min, 1.7 g/10 min, 1.8 g/10 min, 1.9 g/10 min, 2.0 g/10 min, 2.1 g/10 min, 2.2 g/10 min, 2.3 g/10 min, 2.4 g/10 min, 2.5 g/10 min, 2.6 g/10 min, 2.7 g/10 min, 2.8 g/10 min, 2.9 g/10 min, 3.0 g/10 min, 3.1 g/10 min, 3.2 g/10 min, 3.3 g/10 min, 3.4 g/10 min, 3.5 g/10 min, 3.6 g/10 min, 3.7 g/10 min, 3.8 g/10 min, 3.9 g/10 min, 4.0 g/10 min, 4.1 g/10 min, 4.2 g/10 min, 4.3 g/10 min, 4.4 g/10 min, 4.5 g/10 min, 4.6 g/10 min, 4.7 g/10 min, 4.8 g/10 min, 4.9 g/10 min, 5.0 g/10 min, 5.1 g/10 min, 5.2 g/10 min, 5.3 g/10 min, 5.4 g/10 min, 5.5 g/10 min, 5.6 g/10 min, 5.7 g/10 min, 5.8 g/10 min, 5.9 g/10 min, 6.0 g/10 min, 6.1 g/10 min, 6.2 g/10 min, 6.3 g/10 min, 6.4 g/10 min, 6.5 g/10 min, 6.6 g/10 min, 6.7 g/10 min, 6.8 g/10 min, 6.9 g/10 min, 7.0 g/10 min, 7.1 g/10 min, 7.2 g/10 min, 7.3 g/10 min, 7.4 g/10 min, 7.5 g/10 min, 7.6 g/10 min, 7.7 g/10 min, 7.8 g/10 min, 7.9 g/10 min, 8.0 g/10 min, 8.1 g/10 min, 8.2 g/10 min, 8.3 g/10 min, 8.4 g/10 min, 8.5 g/10 min, 8.6 g/10 min, 8.7 g/10 min, 8.8 g/10 min, 8.9 g/10 min, 9.0 g/10 min, 9.1 g/10 min, 9.2 g/10 min, 9.3 g/10 min, 9.4 g/10 min, 9.5 g/10 min, 9.6 g/10 min, 9.7 g/10 min, 9.8 g/10 min, 9.9 g/10 min, 10.0 g/10 min, 10.1 g/10 min, 10.2 g/10 min, 10.3 g/10 min, 10.4 g/10 min, 10.5 g/10 min, 10.6 g/10 min, 10.7 g/10 min, 10.8 g/10 min, 10.9 g/10 min, 11.0 g/10 min, 11.1 g/10 min, 11.2 g/10 min, 11.3 g/10 min, 11.4 g/10 min, 11.5 g/10 min, 11.6 g/10 min, 11.7 g/10 min, 11.8 g/10 min, 11.9 g/10 min, 12.0 g/10mn, 12.1 g/10 min, 12.2 g/10 min, 12.3 g/10 min, 12.4 g/10 min, 12.5 g/10 min, 12.6 g/10 min, 12.7 g/10 min, 12.8 g/10 min, 12.9 g/10 min, 13.0 g/10 min, 13.1 g/10 min, 13.2 g/10 min, 13.3 g/10 min, 13.4 g/10 min, 13.5 g/10 min, 13.6 g/10 min, 13.7 g/10 min, 13.8 g/10 min, 13.9 g/10 min, 14.0 g/10 min, 14.1 g/10 min, 14.2 g/10 min, 14.3 g/10 min, 14.4 g/10 min, 14.5 g/10 min, 14.6 g/10 min, 14.7 g/10 min, 14.8 g/10 min, 14.9 g/10 min, 15.0 g/10 min, 15.1 g/10 min, 15.2 g/10 min, 15.3 g/10 min, 15.4 g/10 min, 15.5 g/10 min, 15.6 g/10 min, 15.7 g/10 min, 15.8 g/10 min, 15.9 g/10 min, 16.0 g/10 min, 16.1 g/10 min, 16.2 g/10 min, 16.3 g/10 min, 16.4 g/10 min, 16.5 g/10 min, 16.6 g/10 min, 16.7 g/10 min, 16.8 g/10 min, 16.9 g/10 min, 17.0 g/10 min, 17.1 g/10 min, 17.2 g/10 min, 17.3 g/10 min, 17.4 g/10 min, 17.5 g/10 min, 17.6 g/10 min, 17.7 g/10 min, 17.8 g/10 min, 17.9 g/10 min, 18.0 g/10 min, 18.1 g/10 min, 18.2 g/10 min, 18.3 g/10 min, 18.4 g/10 min,
18.5 g/10 min, 18.6 g/10 min, 18.7 g/10 min, 18.8 g/10 min, 18.9 g/10 min, 19.0 g/10 min, 19.1 g/10 min, 19.2 g/10 min, 19.3 g/10 min, 19.4 g/10 min, 19.5 g/10 min, 19.6 g/10 min, 19.7 g/10 min, 19.8 g/10 min, 19.9 g/10 min, and 20.0 g/10 min, as per ISO 1133. In particular embodiments, the HDPE may have an MFR at 190 °C and 5 kg of from 0.5 g/10 min to 5 g/10 min.
[0029] In certain instances, the HDPE may have a MFR at 190 °C and 2.16 kg of from 0.1 g/10 min to 5.0 g/10 min, as per ISO 1133, or at least, equal to, and/or between any two of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1.0 g/10 min, 1.1 g/10 min, 1.2 g/10 min, 1.3 g/10 min, 1.4 g/10 min,
1.5 g/10 min, 1.6 g/10 min, 1.7 g/10 min, 1.8 g/10 min, 1.9 g/10 min, 2.0 g/10 min, 2.1 g/10 min, 2.2 g/10 min, 2.3 g/10 min, 2.4 g/10 min, 2.5 g/10 min, 2.6 g/10 min, 2.7 g/10 min, 2.8 g/10 min, 2.9 g/10 min, 3.0 g/10 min, 3.1 g/10 min, 3.2 g/10 min, 3.3 g/10 min, 3.4 g/10 min,
3.5 g/10 min, 3.6 g/10 min, 3.7 g/10 min, 3.8 g/10 min, 3.9 g/10 min, 4.0 g/10 min, 4.1 g/10 min, 4.2 g/10 min, 4.3 g/10 min, 4.4 g/10 min, 4.5 g/10 min, 4.6 g/10 min, 4.7 g/10 min, 4.8 g/10 min, 4.9 g/10 min and 5.0 g/10.
[0030] In particular embodiments, the HDPE may have a MFR at 190 °C and 21.6 kg of from 10 g/10 min to 35 g/10 min, as per ISO 1133, or at least, equal to, and/or between any two of 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min,
17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min. [0031] The HDPE component may have a poly dispersity index (PDI = Mw/Mn) of from 2 to 25 as determined by high temperature gel permeation chromatography, or at least, equal to, and/or between any two of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, and 25. In certain applications, the PDI may range from 13 to 20, as determined by high temperature gel permeation chromatography.
[0032] Tensile modulus of the HDPE can be from 800 MPa to 1300 MPa, or at least, equal to, and/or between any two of 800 MPa, 850 MPa, 900 MPa, 950 MPa, 1000 MPa, 1050 MPa, 1100 MPa, 1150 MPa, 1200 MPa, 1250 MPa and 1300 MPa, as measured by ISO 527. Tensile strength at yield of the HDPE can be from 20 MPa to 40 MPa, or at least, equal to, and/or between any two of 20 MPa, 25 MPa, 30 MPa, 35 MPa, and 40 MPa, as measured by ISO 527. [0033] The Izod notched impact strength of the HDPE component at -30 °C can be from 3 kJ/m2 to 6 kJ/m2 or at least, equal to, and/or between any two of 3 kJ/m2, 4 kJ/m2, 5 kJ/m2, and 6 kJ/m2. The Izod notched impact strength of the HDPE component at 23 °C can be from 10 kJ/m2 to 22 kJ/m2 or at least, equal to, and/or between any two of 10 kJ/m2, 11 kJ/m2, 12 kJ/m2, 13 kJ/m2, 14 kJ/m2, 15 kJ/m2, 16 kJ/m2, 17 kJ/m2, 18 kJ/m2, 19 kJ/m2, 20 kJ/m2, 21 kJ/m2 22 kJ/m2, 23 kJ/m2, 24 kJ/m2, 25 kJ/m2, 26 kJ/m2, 27 kJ/m2, 28 kJ/m2, 29 kJ/m2 and 30 kJ/m2 as measured by ISO 180.
[0034] The HDPE component, as described above, is used as a polymer blend in combination with one or more different optics-enhancing additives used to provide the increased transparency and/or reduced haze. The lack of transparency and/or haze of HDPE is the result of light scattering that results in the opaque or translucent appearance of the HDPE. This is largely attributed to the large amount of crystalline spherulites present in the HDPE material, which scatter the light.
[0035] The optics-enhancing additives may include one or more monomeric and/or polymeric additives that are partially and/or fully dispersible within the HDPE. Such additives will hereinafter be referred to as “dispersible additives,” “dispersible monomeric and/or polymeric additives,” “dispersible monomeric additives,” “dispersible polymeric additives” or similar expressions unless it is otherwise stated or is apparent from the context. Such “dispersible additives” include those that are both partially dispersible and fully dispersible within the HDPE materials. These dispersible additives may be used in combination with a further optics enhancing additive of a clarifying and/or nucleating agent. The addition of these additives is believed to reduce the size and/or modify the shape of the crystalline spherulites in the HDPE composition when the melt blend begins to crystallize, such as during the molding of the HDPE article, thereby leading to the lowering of percentage crystallinity and/or the lowering of size of crystalline spherulites and/or the alteration of the shape of crystalline spherulites. This is true even though the additives are added during melt mixing of the HDPE during the extrusion process.
[0036] These optics-enhancing additives may be selected and used in amounts so that the processability, flow properties, and mechanical properties remain mainly unaffected, while the optical properties are improved. This is important because in addition to the optic-enhancing additives reducing the size and/or altering the shape of the crystalline spherulites, the optic enhancing additives may also lower the overall percentage crystallinity of the HDPE composition by 30% to 80% of its original value without the use of the optics-enhancing additives. In particular embodiments, the optic-enhancing additives may lower the overall percentage crystallinity of the HDPE composition by at least equal to, and/or between any two of 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%,
45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%,
61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%,
77%, 78%, 79%, and 80% of its original value without the use of the optics-enhancing additives. While a reduction in crystallinity may increase the transparency and/or reduce haze of the HDPE composition, such reduction in crystallinity can also negatively impact its processability, flow properties, and mechanical properties. Therefore, a careful balance must be maintained so that the decrease in crystallinity of the HDPE composition does not significantly alter its processability and flow properties, and perhaps more importantly, its final mechanical properties, such as its ESCR performance, which is critical for the HDPE composition being useful in commercial applications.
[0037] The optics-enhancing dispersible additive is one that is either partially soluble or partially miscible with the HDPE material under the processing conditions used in forming the HDPE composition or one that is fully soluble or fully miscible with the HDPE material under the processing conditions used in forming the HDPE composition. As used herein, the terms “soluble” or “miscible” and variations of these terms may be used interchangeably unless otherwise apparent from its context. Partial solubility or partial miscibility refers to those materials that do not form distinct domain morphology, but rather form a co-continuous morphology or no distinction can be made in transmission electron microscopy (TEM) and/or scanning electron microscopy (SEM) analyses. [0038] The dispersible additives, which may be any one or a combination of two or more different monomeric and/or polymeric additives that are partially and/or fully dispersible within the HDPE, may be used in an amount of from 0.1 wt.% to 5 wt.% by total weight of the HDPE composition. In particular embodiments, the total amount of the dispersible additives used may be at least, equal to, and/or between any two of 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt.%, 1.1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 1.7 wt.%, 1.8 wt.%, 1.9 wt.%, 2.0 wt.%, 2.1 wt.%, 2.2 wt.%, 2.3 wt.%, 2.4 wt.%, 2.5 wt.%, 2.6 wt.%, 2.7 wt.%, 2.8 wt.%, 2.9 wt.%, 3.0 wt.%, 3.1 wt.%, 3.2 wt.%, 3.3 wt.%, 3.4 wt.%, 3.5 wt.%, 3.6 wt.%, 3.7 wt.%, 3.8 wt.%, 3.9 wt.%, 4.0 wt.%, 4.1 wt.%, 4.2 wt.%, 4.3 wt.%, 4.4 wt.%, 4.5 wt.%, 4.6 wt.%, 4.7 wt.%, 4.8 wt.%, 4.9 wt.%, and 5.0 wt.% by total weight of the HDPE composition.
[0039] Non-limiting examples of suitable partially or fully dispersible monomers for use as the optic-enhancing additive include monomeric long-alkyl-chain-containing phase change materials such as methyl laurate, 1 -decanol, and tetradecane. Such dispersible monomers get dispersed within the HDPE matrix and interfere or co-crystallize with the crystallization of the HDPE component during solidification of the polymer melt.
[0040] Non-limiting examples of suitable partially or fully dispersible polymers for use as the optic-enhancing additive include low density polyethylenes (LDPE), linear low density polyethylenes (LLDPE), branched polyethylenes, low molecular weight high density polyethylenes, ultrahigh molecular weight polyethylenes (UHMWPE), polyolefin elastomers (POE), polyolefin plastomers (POP), and maleic anhydride grafted polyethylenes. Most of these polymers contain ethylene blocks that facilitate their dispersibility or miscibility with the HDPE component.
[0041] In particular embodiments, the LDPE used as the dispersible polymeric additive may be that have a density ranging from 0.910 kg/m3 to 0.925 kg/m3 as per ASTM D1505. The LDPE may have melt flow rate of from 10 g/10 min to 40 g/10 min at 190°C and with 2.16 Kg load. In particular embodiments, the LDPE may have a melt flow rate of from at least, equal to, and/or between any two melt flow rate of 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min, 36 g/10 min, 37 g/10 min, 38 g/10 min, 39 g/10 min, and 40 g/10 min at 190°C and with 2.16 Kg load. [0042] In particular embodiments, the LLDPE used as the dispersible polymeric additive may be that have a density ranging from 0.910 kg/m3 to 0.940 kg/m3 as per ASTM D1505. The LLDPE may have melt flow rate of from 1 g/10 min to 40 g / 10 min at 190°C and with 2.16 Kg load. In particular embodiments, the LLDPE may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min, 36 g/10 min, 37 g/10 min, 38 g/10 min, 39 g/10 min, and 40 g/10 min at 190°C and with 2.16 Kg load.
[0043] In certain applications, the branched polyethylene used as the dispersible polymeric additive may be LDPE or HDPE that have a density ranging from 0.90 kg/m3 to 0.97 kg/m3 as per ASTM D1505. The branched polyethylene may have melt flow rate of from 0.1 g/ 10 min to 40 g / 10 min at 190°C and with 2.16 Kg load. In particular embodiments, the branched polyethylene may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min, 36 g/10 min, 37 g/10 min, 38 g/10 min, 39 g/10 min, and 40 g/10 min at 190°C and with 2.16 Kg load.
[0044] In certain instances, the low molecular weight high density polyethylene used as the dispersible polymeric additive may be that having a density of from 940 kg/m3 or 945 kg/m3 to 965 kg/m3 as per ASTM D1505. The low molecular weight high density polyethylene may have melt flow rate of from 1 g/ 10 min to 40 g / 10 min at 190°C and with 2.16 Kg load. In particular embodiments, the low molecular weight high density polyethylene may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min, 36 g/10 min, 37 g/10 min, 38 g/10 min, 39 g/10 min, and 40 g/10 min at 190°C and with 2.16 Kg load.
[0045] In particular embodiments, the ultrahigh molecular weight polyethylene (UHMWPE) used as the dispersible polymeric additive may be that having a density of from 930 kg/m3 to 950 kg/m3 as per ASTM D1505. The UHMWPE may have melt flow rate of from 0.1 g/ 10 min to 5 g/ 10 min at 190°C and with 21.6 Kg load. In particular embodiments, the UHMWPE may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1.0 g/10 min, 1.1 g/10 min, 1.2 g/10 min, 1.3 g/10 min, 1.4 g/10 min, 1.5 g/10 min, 1.6 g/10 min, 1.7 g/10 min, 1.8 g/10 min, 1.9 g/10 min, 2.0 g/10 min, 2.1 g/10 min, 2.2 g/10 min, 2.3 g/10 min, 2.4 g/10 min, 2.5 g/10 min, 2.6 g/10 min, 2.7 g/10 min,
2.8 g/10 min, 2.9 g/10 min, 3.0 g/10 min, 3.1 g/10 min, 3.2 g/10 min, 3.3 g/10 min, 3.4 g/10 min, 3.5 g/10 min, 3.6 g/10 min, 3.7 g/10 min, 3.8 g/10 min, 3.9 g/10 min, 4.0 g/10 min, 4.1 g/10 min, 4.2 g/10 min, 4.3 g/10 min, 4.4 g/10 min, 4.5 g/10 min, 4.6 g/10 min, 4.7 g/10 min,
4.8 g/10 min, 4.9 g/10 min, and 5.0 g/10 min at 190°C and with 21.6 Kg load.
[0046] In particular embodiments, the polyolefin elastomer (POE) used as the dispersible polymeric additive may be that having a density of from 840 kg/m3 to 930 kg/m3 as per ASTM D1505. The POE may have melt flow rate of from 0.1 40 g/ 10 min to 40 g / 10 min at 190°C and with 2.16 Kg load. In particular embodiments, the POE may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min, 36 g/10 min, 37 g/10 min, 38 g/10 min, 39 g/10 min, and 40 g/10 min at 190°C and with 2.16 Kg load. [0047] In some applications, the polyolefin plastomer (POP) used as the dispersible polymeric additive may be that having a density of from 850 kg/m3 to 920 kg/m3 as per ASTM D1505. The POP may have melt flow rate of from 0.1 g/ 10 min to 40 g / 10 min at 190°C and with 2.16 Kg load. In particular embodiments, the POP may have a melt flow rate of from at least, equal to, and/or between any melt flow rate of 0.1 g/10 min, 0.2 g/10 min, 0.3 g/10 min, 0.4 g/10 min, 0.5 g/10 min, 0.6 g/10 min, 0.7 g/10 min, 0.8 g/10 min, 0.9 g/10 min, 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min, 36 g/10 min, 37 g/10 min, 38 g/10 min, 39 g/10 min, and 40 g/10 min at 190°C and with 2.16 Kg load.
[0048] In certain instances, the maleic anhydride grafted polyethylene used as the dispersible polymeric additive may be that having a density ranging from 0.910 kg/m3 to 0.960 kg/m3 as per ASTM D1505. The maleic anhydride grafted polyethylene may have melt flow rate of from 1 g/ 10 min to 40 g/ 10 min at 190°C and with 2.16 Kg load. In particular embodiments, the maleic anhydride grafted polyethylene may have a melt flow rate of from at least, equal to, and/or between any two melt flow rate of 1 g/10 min, 2 g/10 min, 3 g/10 min, 4 g/10 min, 5 g/10 min, 6 g/10 min, 7 g/10 min, 8 g/10 min, 9 g/10 min, 10 g/10 min, 11 g/10 min, 12 g/10 min, 13 g/10 min, 14 g/10 min, 15 g/10 min, 16 g/10 min, 17 g/10 min, 18 g/10 min, 19 g/10 min, and 20 g/10 min, 21 g/10 min, 22 g/10 min, 23 g/10 min, 24 g/10 min, 25 g/10 min, 26 g/10 min, 27 g/10 min, 28 g/10 min, 29 g/10 min, 30 g/10 min, 31 g/10 min, 32 g/10 min, 33 g/10 min, 34 g/10 min, and 35 g/10 min, 36 g/10 min, 37 g/10 min, 38 g/10 min, 39 g/10 min, and 40 g/10 min n at 190°C and with 2.16 Kg load.
[0049] The optics-enhancing additive of a clarifying and/or nucleating agent may be used in combination with dispersible additives discussed above. Nucleating agents may be considered as those additives that are added to polymers to facilitate crystal growth in the polymer melt. Those nucleating agents that can be classified as clarifying agents also facilitate crystal growth, but the crystal growth is reduced in comparison to nucleating agents that can be classified as non-clarifying nucleating agents, leading to a reduction in the size and shape of the crystalline spherulite of semi-crystalline polymers. As used herein, unless otherwise specified, the term “clarifying agent” and similar expressions are meant to encompass those nucleating agent compounds that facilitate crystal growth where the crystal growth results in a reduced crystalline spherulite size from those that would result without the clarifying agent. Where the term “nucleating agent” and similar expressions are used, unless otherwise specified, it is meant to include those compounds that form nuclei for facilitating crystal growth in the polymer melt with or without reducing the size of the crystalline spherulites. Such nucleating agents would broadly cover clarifying agents, as well. The expression “non-clarifying nucleating agent” and similar expressions is meant to encompass those nucleating agents that do not normally reduce the size of the crystalline spherulites or that would not be classified as a clarifying agent. [0050] While clarifying and/or nucleating agents have been commonly used with such materials as polypropylene (PP), polyethylene terephthalate (PET), nylon, etc., they have not been used commercially with polyethylene. This is because polyethylene has a very high crystallization rate and kinetics. The rate of crystallization is difficult to control compared to other polymers. Furthermore, HDPE has a relatively high percentage crystallinity compared to these other polymers, such that the use of nucleating agents is not necessary.
[0051] When used in specific amounts in forming the HDPE compositions described herein, the clarifying and/or nucleating agents have been shown to increase the transparency and/or reduce haze in the HDPE compositions without significantly affecting the crystallinity of the HDPE composition to a degree that the desired flow characteristics, processability, and mechanical properties are significantly altered. This is particularly true when used in combination with the dispersible additives, as discussed previously, where they may have a synergistic effect. The amount of the clarifying and/or nucleating agents may range from 50 ppm to 500 ppm by total weight of the HDPE composition. In particular embodiments, the clarifying and/or nucleating agent may be used in an amount of from at least, equal to, and/or between any two of 50 ppm, 51 ppm, 52 ppm, 53 ppm, 54 ppm, 55 ppm, 56 ppm, 57 ppm, 58 ppm, 59 ppm, 60 ppm, 61 ppm, 62 ppm, 63 ppm, 64 ppm, 65 ppm, 66 ppm, 67 ppm, 68 ppm, 69 ppm, 70 ppm, 71 ppm, 72 ppm, 73 ppm, 74 ppm, 75 ppm, 76 ppm, 77 ppm, 78 ppm, 79 ppm, 80 ppm, 81 ppm, 82 ppm, 83 ppm, 84 ppm, 85 ppm, 86 ppm, 87 ppm, 88 ppm, 89 ppm, 90 ppm, 91 ppm, 92 ppm, 93 ppm, 94 ppm, 95 ppm, 96 ppm, 97 ppm, 98 ppm, 99 ppm, 100 ppm, 105 ppm, 110 ppm, 115 ppm, 120 ppm, 125 ppm, 130 ppm, 135 ppm, 140 ppm, 145 ppm, 150 ppm, 155 ppm, 160 ppm, 165 ppm, 170 ppm, 175 ppm, 180 ppm, 185 ppm, 190 ppm, 195 ppm, 200 ppm, 205 ppm, 210 ppm, 215 ppm, 220 ppm, 225 ppm, 230 ppm, 235 ppm, 240 ppm, 245 ppm, 250 ppm, 255 ppm, 260 ppm, 265 ppm, 270 ppm, 275 ppm, 280 ppm, 285 ppm, 290 ppm, 295 ppm, 300 ppm, 305 ppm, 310 ppm, 315 ppm, 320 ppm, 325 ppm, 330 ppm, 335 ppm, 340 ppm, 345 ppm, 350 ppm, 355 ppm, 360 ppm, 365 ppm, 370 ppm, 375 ppm, 380 ppm, 385 ppm, 390 ppm, 395 ppm, 400 ppm, 405 ppm, 410 ppm, 415 ppm, 420 ppm, 425 ppm, 430 ppm, 435 ppm, 440 ppm, 445 ppm, 450 ppm, 455 ppm, 460 ppm, 465 ppm, 470 ppm, 475 ppm, 480 ppm, 485 ppm, 490 ppm, 495 ppm, and 500 ppm by total weight of the HDPE composition. [0052] Non-limiting examples of suitable nucleating agents include calcium salts of dicarboxylic acid, metal salts of cyclohexane dicarboxylic acid, bisamide, lithium carbonate, benzoic acid, inorganic oxides, nano- zinc oxides, talc, clay, powdered polymeric agents such as polyphenylene oxide, polyvinylenedifluoride, polycarbonate, polycarbonate-siloxane copolymer, cross-linked polycarbonate, polyetherimide, polyamide, ethylene propylene diene monomer, and polyoxymethylene. A non-limiting example of a suitable commercially available nucleating agent is that available as HYPERFORM™ HPN-20E, available from Milliken & Company, which is a calcium salt of cyclohexane dicarboxylic acid.
[0053] Non-limiting examples of suitable clarifying agents include sorbitol derivatives,
1.2.3.4-bis-dibenzylidene sorbitol (DBS), l,2,3,4-bis-(p-methoxybenzylidene sorbitol) (DOS),
1.2.3.4-bis-(3,4-dimethylbenzylidene sorbitol) (MBDS), and l,3:2,4-di(3,4- dimethylbenzylidene) sorbitol (DMDBS).
[0054] The polyethylene compositions can further include at least one additional optional or secondary additive, as distinguished from the optics-enhancing dispersible additives and clarifying and/or nucleating agents discussed above. Such optional or secondary additives may be those that do not necessarily impact or increase the transparency or haze of the final product. Non-limiting examples of additional optional or secondary additives include a heat conductive agent, a tie agent, an antiblocking agent, an antistatic agent, an antioxidant, a neutralizing agent, an acid scavenger, a blowing agent, a dye, a flame retardant agent, a filler (hard or soft), an impact modifier, a mold release agent, an oil, another polymer, a pigment, a processing agent, a reinforcing agent, a stabilizer (including light stabilizers), an UV resistance agent, a slip agent, a flow modifying agent, and combinations thereof.
[0055] In some instances, a heat conductive additive is present in the polymer blend in an amount of at least, equal to, and/or between any two of 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 1.0 wt. % by total weight of the polymer blend. Non-limiting examples of heat conductive additive include, aluminum oxide, titanium dioxide, graphitic compounds, graphenes, boron nitride, aluminum nitride, zinc oxide [0056] In certain aspects, a tie molecule is present in the polymer blend in amount of at least, equal to, and/or between any two of 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 1.0 wt. % by total weight of the polymer blend. Non- limiting examples of tie molecules include, linear low-density polyethylene, low-density polyethylene, and medium density polyethylene.
[0057] In some embodiments, a filler is present in the polymer blend in amount of at least, equal to, and/or between any two of 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt. %, 2.0 wt. %, 3.0 wt. %, 4.0 wt. %, 5.0 wt. %, 6.0 wt. %, 7.0 wt. %, 8.0 wt. %, 9.0 wt. %, 10.0 wt. %, 20.0 wt. %, 30.0 wt. % by total weight of the polymer blend. The filler can be a hard filler. Non-limiting examples of hard filler include, inorganic particulate fillers such as silica, calcium carbonate, inorganic layered fillers such as clays, mica. The filler can be a soft filler. Non-limiting examples of soft filler include, immiscible particulate elastomeric/polymeric resins. The filler can also be a hollow filler. Non limiting examples of hollow filler include, glass microspheres, plastic microspheres, ceramic microspheres such as cenospheres made up of alumino silicate microspheres, metallic microspheres made up of aluminum and copper/silver microspheres, and phenolic microspheres.
[0058] In certain aspects, a light stabilizer is present in the polymer blend in an amount of at least, equal to, and/or between any two of 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 1.0 wt. % by total weight of the polymer blend. The light stabilizer can be a hindered amine light stabilizer. The term “hindered amine light stabilizer” refers to a class of amine compounds having certain light stabilizing properties. Non-limiting examples, of hindered amine light stabilizers (HALS) include 1-cyclohexyloxy- 2,2,6,6-tetramethyl-4-octadecylaminopiperidine; bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(l-acetoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(l,2,2,6,6- pentamethylpiperidin-4-yl) sebacate; bis(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(l-acyl-2, 2,6,6- tetramethylpiperidin-4-yl) sebacate; bis(l,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di- tert-butyl-4-hydroxybenzyl malonate; 2,4-bis[(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin- 4-yl)butylamino]-6-(2-hydroxyethyl amino-s-triazine; bis(l-cyclohexyloxy-2, 2,6,6- tetramethylpiperidin-4-yl) adipate; 2,4-bis[(l-cyclohexyloxy-2,2,6,6-piperidin-4- yl)butylamino]-6-chloro-s-triazine; l-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6- tetramethylpiperidine; l-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine; l-(2-hydroxy-2-methyl propoxy)-4-octadecanoyloxy-2,2,6,6-tetramethyl piperidine; bis(l-(2- hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;bis(l-(2-hydroxy-2- methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) adipate; 2, 4-bis{N-[l-(2 -hydroxyl- methyl propoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2- hydroxyethylamino)-s-triazine; 4-benzoyl-2,2,6,6-tetramethylpiperidine; di-(l,2,2,6,6- pentamethylpiperidin-4-yl) p-methoxybenzylidenemalonate ; 2 ,2 , 6 ,6-tetr amethylpiperidin-4-yl octadecanoate; bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate; 1,2,2,6,6-pentamethyl- 4-aminopiperidine; 2-undecyl-7,7,9,9-tetramethyl-l-oxa-3,8-diaza-4-oxo-spiro[4,5]decane; tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate; tris(2-hydroxy-3-(amino-(2, 2,6,6- tetramethylpiperidin-4-yl)propyl) nitrilotriacetate; tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-
1.2.3.4-butane-tetracarboxylate; tetrakis(l, 2,2,6, 6-pentamethyl-4-piperidyl)-l, 2,3, 4-butane- tetracarboxylate; 1 , 1 '-(1 ,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone); 3-n-octyl-
7,7,9,9-tetramethyl-l,3,8-triazaspiro[4.5]decan-2,4-dione; 8-acetyl-3-dodecyl-7,7,9,9- tetramethyl-l,3,8-triazaspiro[4.5]decane-2,4-dione; 3-dodecyl-l -(2, 2, 6, 6-tetramethyl-4- piperidyl)pyrrolidin-2,5-dione; 3-dodecyl-l -(1, 2,2,6, 6-pentamethyl-4-piperidyl)pyrrolidine- 2,5-dione; N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine; reaction product of 2,4-bis[(l-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s- triazine with N,N'-bis(3-aminopropyl)ethylenediamine);condensate of 1 -(2 -hydroxy ethyl)- 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; condensate of N, N'-bis(2, 2,6,6- tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro- 1,3,5- triazine; condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-l,3,5-triazine; condensate of N,N'-bis-(2,2,6,6-tetramethyl- 4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-l,3,5-triazine; condensate of N,N'-bis-(l ,2,2,6, 6-pentamethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6- dichloro-l,3,5-triazine; condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethyl piperidyl)-l,3,5-triazine and l,2-bis(3-aminopropylamino)ethane; condensate of 2-chloro-4,6- di-(4-n-butylamino-l,2,2,6,6-pentamethylpiperidyl)-l,3,5-triazine and l,2-bis-(3- aminopropylamino)ethane; a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-l-oxa- 3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin; poly| methyl, (3-oxy-(2, 2,6,6- tetramethylpiperidin-4-yl)propyl)]siloxane, CAS#182635-99-0; reaction product of maleic acid anhydride-C18-C22-a-olefin-copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine; oligomeric condensate of 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and
2.4-dichloro-6-[(2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2- chloro-4,6-bis(dibutylamino)-s-triazine; oligomeric condensate of 4,4'- hexamethylenebis(amino-l,2,2,6,6-pentaamethylpiperidine) and 2,4-dichloro-6-[(l,2,2,6,6- pentaamethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6- bis(dibutylamino)-s-triazine; oligomeric condensate of 4,4'-hexamethylenebis(amino-l- propoxy-2,2,6,6-tetramethyl piperidine) and 2,4-dichloro-6-[(l-propoxy-2,2,6,6- tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6- bis(dibutylamino)-s-triazine; oligomeric condensate of 4,4'-hexamethylenebis(amino-l- acyloxy-2,2,6,6-tetramethyl piperidine) and 2,4-dichloro-6-[(l-acyloxy-2,2,6,6- tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6- bis(dibutylamino)-s-triazine; and product obtained by reacting (a) with (b) where (a) is product obtained by reacting l,2-bis(3-aminopropylamino)ethane with cyanuric chloride and (b) is (2,2,6,6-tetramethyl piperidin-4-yl)butylamine. Also included are the sterically hindered N-H, N-methyl, N-methoxy, N-hydroxy, N-propoxy, N-octyloxy, N-cyclohexyloxy, N-acyloxy and N-(2-hydroxy-2-methylpropoxy) analogues of any of the above-mentioned compounds. Non limiting examples of commercial light stabilizer are available from BASF under the trade name Uvinul® 4050H, 4077H, 4092H, 5062H, 5050H, 4092H, 4077H, 3026, 3027, 3028, 3029, 3033P, and 3034 or Tinuvin® 622.
[0059] Anti-static agents can be used to inhibit accumulation of dust on plastic articles. Antistatic agents can improve the electrical conductivity of the plastic compositions, and thus dissipate any surface charges, which develop during production and use. Thus, dust particles are less attracted to the surface of the plastic article, and dust accumulation is consequently reduced. In certain aspects of the present invention, the antistatic agent can be a glycerol monostearate. The polymer blend can include an anti-static agent in an amount of at least, equal to, and/or between any two 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 1 wt. % by total weight of the polymer blend.
[0060] A lubricant can be added to a polymer blend to improve the mold-making characteristics. The lubricant can be a low molecular compound from a group of fatty acids, fatty acid esters, wax ester, fatty alcohol ester, amide waxes, metal carboxylate, montanic acids, montanic acid ester, or such high molecular compounds, as paraffins or polyethylene waxes. In certain aspects of the present invention, the lubricant is a metal stearate. Non-limiting examples of metal stearates include zinc stearate, calcium stearate, lithium stearate or a combination thereof, preferably calcium stearate. The polymer blend can include a lubricant in an amount of at least, equal to, and/or between any two of 0.01 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 1 wt. % by total weight of the polymer blend.
[0061] An antioxidant can provide protection against polymer degradation during processing. Phosphites are known thermal oxidative stabilizing agents for polymers and other organic materials. The antioxidant can be a phosphite-based antioxidant. In certain aspects phosphite- antioxidants include, but are not limited to, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite tristearyl sorbitol triphosphite, and tetrakis(2,4-di-tertbutylphenyl)-4,4'-biphenylene diphosphonite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite. The polymer blend can include an antioxidant in an amount of at least, equal to, and/or between any two of 0.01 wt.%, 02 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, and 0.1 wt. % by total weight of the polymer blend. Non-limiting examples of commercially available antioxidants include Irganox 1010 available from BASF, or Doverphos S9228T available from Dover Chemical Company.
[0062] In forming the HDPE composition, the various components of the HDPE, the optics enhancing dispersible additive and clarifying and/or nucleating agent, as described, along with any additional optional additives, can be dry blended. The HDPE component may be in the form of pellets, powder, flakes or fluff. The materials are combined in a customary mixing machine, in which the HDPE, optics-enhancing additives, and nucleating agents are mixed with any optional additional or secondary additives. The optional additional additives can be added at the end or during the processing steps to produce the polymer blend. Suitable machines for such mixing are known to those skilled in the art. Non-limiting examples include mixers, kneaders and extruders. These materials are then fed directly into the feed zone of an extruder. In certain cases, the process can be carried out in an extruder and introduction of the additives may occur during processing. Non-limiting examples of suitable extruders include single screw extruders, counter-rotating and co-rotating twin-screw extruders, planetary-gear extruders, ring extruders, or co-kneaders. The process can be performed at a temperature from 160 °C to 300 °C.
[0063] In some embodiments, the HDPE, optics-enhancing additives of the dispersible additive and clarifying and/or nucleating agents, and any optional secondary additives, used to produce the polymer blend of the present invention can be melt-extruded by following typical procedures of weighing the required amounts of the HDPE and additives, followed by dry blending, and then feeding the mixture into a main feeder of a twin-screw co-rotating extruder (length/diameter (L/D) ratio of 25:1 or 40:1) to obtain the final composition. The HDPE, additives, or blend thereof can be subjected to an elevated temperature for a sufficient period of time during blending. The blending temperature can be above the softening point of the polymers. In certain aspects, the extrusion process can be performed at a temperature from 160 °C to 300 °C. The optics-enhancing dispersible additives and clarifying and/or nucleating agents can be added along with other optional additives in-line and prior to pelletization of the HDPE resin during the production process. The amounts of additives combined with the HDPE can be adjusted to provide those weight amounts previously discussed.
[0064] The optional secondary additives can be premixed or added individually to the polymer blend or the different components thereof. By way of example, the secondary additives of the present invention can be premixed such that the blend is formed prior to adding it to the HDPE or the optics-enhancing additives. The blend thereof can be subjected to an elevated temperature for a sufficient period of time during blending and/or incorporation of additives. Incorporation of optional secondary additives into the polymer resin can be carried out, for example, by mixing the above-described components using methods customary in process technology. The blending temperature can be above the softening point of the polymers. In certain aspects, a process can be performed at a temperature from 160 °C to 300 °C. Such “melt mixing” or “melt compounding” results in uniform dispersion of the present optional additives in the HDPE and/or optic-enhancing additives.
[0065] Articles (e.g., caps, bottles and containers) that are manufactured from the blend of HDPE and optics-enhancing additives can have a higher transparency and/or reduced haze than articles of manufacture made from HDPE without such additives. In particular, the HDPE composition may have a transparency of from 80% or more and a haze of from 60% or less as determined by ASTM D1003 at a thickness of from 1 mm or more, with or without any drawing, stretching or orienting of the HDPE composition. In certain instances the HDPE composition may have a transparency of at least, equal to, and/or between any two of 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%,
97%, 98%, 99%, and 100%, as determined by ASTM D1003 at a thickness of from 1 mm or more, with or without any drawing, stretching or orienting of the HDPE composition. The haze of the HDPE composition may be from at least equal to, and/or between any two of 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 29%, 30%, 31%, 32%, 33%, 34%, 35%,
36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%,
52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, and 60%, as determined by ASTM D1003 at a thickness of from 1 mm or more, with or without any drawing, stretching or orienting of the HDPE composition. In some embodiments, the transparency of the HDPE composition may provide an article with a transparency of from 90% or more and a haze of from 50% or less as determined by ASTM D1003 at a thickness of from 1 mm or more, with or without any drawing, stretching or orienting the HDPE composition. [0066] The polymer blend compositions formed as described are normally collected as pellets, which can be stored for a time or employed immediately in a forming process. The forming processes can include injection molding, blow molding, compression molding, sheet extrusion, film blowing, pipe extrusion, profile extrusion, calendaring, thermoforming, rotomolding, or combinations thereof. The final formed articles can be, for instance, molded parts, sheets, films, or fibers. Examples of molded parts include a cap, a bottle cap, a container, a bottle, a lid, a sheet, a pipe, a pipe coupling, a bottle, a cup, a tray, a pallet, or a toy, or combinations thereof. Caps can be injection and/or compression molded. The caps may be threaded or non- threaded caps for selectively closing off openings to bottles or other containers. Such caps can be used in a variety of food and non-food applications. By way of example, caps and containers that include the polymer blend of the present invention can be used with containers for storing carbonated beverages, pressurized beverages, or the like.
[0067] The following examples serve to further illustrate various embodiments and applications.
EXAMPLES
EXAMPLE 1
[0068] Different optics-enhancing additives comprising an optic-enhancing partially soluble or fully soluble monomeric and/or polymeric additive in combination with clarifying and/or nucleating agents for increasing the transparency and/or reducing haze in HDPE. The HDPE compositions were prepared using SABIC® HDPE B5823, which is a unimodal HDPE having an MFR at 190° C and 5 kg of 0.9 g/ 10 min and a density of 958 kg/m3. Different optics enhancing additives for increasing the transparency and/or reducing haze in HDPE were used with the B5823 HDPE. Both transparency and haze of the HDPE samples were measured using a Haze-Guard Plus transparency meter, available from BYK Gardner, according to ASTM D1003. For comparison purpose, neat B5823 HDPE without any optics-enhancing additives, was also extruded and tested for its optical properties. The different mixtures were fed into a hopper of aZSK-25 mm 10-barrel twin-screw extruder with an L/D ratio of 25:1. The operating parameters used are set forth in Table 1 below. Table 1
Figure imgf000025_0001
[0069] The torque measured during the melt extrusion of the neat and formulated HDPE with optics-enhancing partially soluble or fully soluble monomeric and/or polymeric additives in combination with clarifying and/or nucleating agents was in the range of 34% - 36%, indicating that the processability of HDPE was not hampered significantly with the incorporation of optics-enhancing additives. [0070] The pellets obtained after the melt extrusion of Example 1 were compression molded into 1.2 mm thick sheets at a temperature of 195 °C to 210 °C, with a holding time of 5 min and a cooling time of 5 min. No visual inhomogeneity was evident in the compression molded sheets. The compression molded sheets, both the neat and formulated HDPE, were then evaluated for optical performance according to ASTM D1003 method. [0071] The % transmittance (%T) value of 1.2 thick compression molded sheet, along with that of blends of HDPE B5823 and different optics-enhancing additives, such as LLDPE, LDPE and tetradecane, in combination of different nucleating agents such as HPN 20E (calcium salt of cyclohexane dicarboxylic acid) and sorbitol, are presented in the Table 2 below. Table 2
Figure imgf000026_0001
[0072] While the invention has been shown in some of its for s, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes and modifications without departing from the scope of the invention based on experimental data or other optimizations considering the overall economics of the process. Accordingly, it is appropriate that the appended claims be construed broadly and, in a manner, consistent with the scope of the invention.

Claims

CLAIMS We claim:
1. A high-density polyethylene (HDPE) composition having increased transparency and/or reduced haze, the composition comprising a mixture of a HDPE, a monomeric and/or polymeric additive that is partially and/or fully dispersed within the HDPE, and a clarifying and/or nucleating agent in an amount of 50 ppm to 500 ppm by total weight of the HDPE composition, the HDPE composition having at least one of a transparency of from 80% or more and a haze of from 60% or less as determined by ASTM D1003 at a thickness of from 1 mm or more.
2. The composition of claim 1, wherein: the HDPE composition has at least one of a transparency of from 90% or more and a haze of from 50% or less as determined by ASTM D1003 at a thickness of from 1 mm or more, without drawing, stretching or orienting the HDPE composition.
3. The composition of any of cl aims 1-2, wherein: the HDPE is at least one of a unimodal, bimodal, and multimodal HDPE.
4. The composition of any of cl aims 1-3, wherein: the HDPE has at least one of: an average molecular weight (Mw) of from 130,000 to 300,000 as determined by high temperature gel permeation chromatography; a poly dispersity index (PDI = Mw/Mn) of from 2 to 25 as determined by high temperature gel permeation chromatography; a melt flow rate (MFR) at 190 °C and 5 kg of from 0.1 g/10 min to 20 g/10 min as per ISO 1133; and a density of from 940 kg/m3 to 965 kg/m3 as per ASTM D1505.
5. The composition of any of claims 1-4, wherein: the monomeric and/or polymeric additive is present in an amount of from 0.1 wt.% to 5 wt.% by total weight of the HDPE composition.
6. The composition of any of cl aims 1-5, wherein: the monomeric and/or polymeric additive is selected from at least one of a monomeric phase change material, methyl laurate, 1-decanol and tetradecane, a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a branched polyethylene, a low molecular weight high density polyethylene, an ultrahigh molecular weight polyethylene (UHMWPE), a polyolefin elastomer (POE), a polyolefin plastomer (POP), maleic anhydride grafted polyethylene, and combinations thereof.
7. The composition of any of cl aims 1-6, wherein: the clarifying and/or nucleating agent is present in an amount of 100 ppm to 200 ppm by total weight of the HDPE composition.
8. The composition of any of cl aims 1-7, wherein: the clarifying and/or nucleating agent is selected from at least one of a sorbitol derivative, 1,2,3,4-bis-dibenzylidene sorbitol (DBS), l,2,3,4-bis-(p-methoxybenzylidene sorbitol) (DOS), l,2,3,4-bis-(3,4-dimethylbenzylidene sorbitol) (MBDS), and l,3:2,4-di(3,4- dimethylbenzylidene) sorbitol (DMDBS), a calcium salt of dicarboxylic acid, a metal salt of cyclohexane dicarboxylic acid, a bisamide, a lithium carbonate, a benzoic acid, an inorganic oxide, nano-zinc oxide, talc, clay, a powdered polymeric agent, polyphenylene oxide, polyvinylenedifluoride, polycarbonate, polycarbonate- siloxane copolymer, cross-linked polycarbonate, polyetherimide, polyamide, ethylene propylene diene monomer, and polyoxymethylene.
9. The composition of any of cl ai 1-8, wherein: the HDPE is a copolymer with comonomers selected from C3 to C10 olefin monomers, the comonomers being present in the HDPE copolymer in an amount of from 2 wt.% or less.
10. The composition of any of claims 1-9, further comprising: at least one of a heat conductive agent, a tie agent, an antiblocking agent, an antistatic agent, an antioxidant, a neutralizing agent, an acid scavenger, a blowing agent, a crystallization aid, a dye, a flame retardant agent, a filler, a hard filler, a soft filler, an impact modifier, a mold release agent, an oil, another polymer, a pigment, a processing agent, a reinforcing agent, a stabilizer, a light stabilizer, an UV resistance agent, a slip agent, a flow modifying agent, and combinations thereof.
11. The composition of any of cl aims 1-10, wherein: the HDPE composition is formed into an article of manufacture.
12. The composition of claim 11, wherein: the article is at least one of a film, a molded part, a container, a beverage container cap, a lid, a sheet, a pipe, a pipe coupling, a bottle, a cup, a tray, a pallet, and a toy.
13. The composition of any of cl aims 11-12, wherein: the article is formed by at least one of injection molding, blow molding, compression molding, sheet extrusion, film blowing, pipe extrusion, profile extrusion, calendaring, and thermoforming.
14. A high-density polyethylene (HDPE) composition having increased transparency and/or reduced haze, the composition comprising a mixture of a HDPE, a monomeric and/or polymeric additive that is partially and/or fully dispersed within the HDPE in an amount of from 0.1 wt.% to 5 wt.% by total weight of the HDPE composition, and a clarifying and/or nucleating agent in an amount of 100 ppm to 500 ppm by total weight of the HDPE composition, the HDPE composition having at least one of a transparency of from 80% or more and a haze of from 40% or less as determined by ASTM D1003 at a thickness of from 1 mm or more, without drawing, stretching or orienting the HDPE composition; and wherein the monomeric and/or polymeric additive is selected from at least one of a monomeric phase change material, methyl laurate, 1-decanol and tetradecane, a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE), a branched polyethylene, a low molecular weight high density polyethylene, an ultrahigh molecular weight polyethylene (UHMWPE), a poly olefin elastomer (POE), a poly olefin plastomer (POP), maleic anhydride grafted polyethylene, and combinations thereof; the clarifying and/or nucleating agent is selected from at least one of a sorbitol derivative, 1,2,3,4-bis-dibenzylidene sorbitol (DBS), l,2,3,4-bis-(p-methoxybenzylidene sorbitol) (DOS), l,2,3,4-bis-(3,4-dimethylbenzylidene sorbitol) (MBDS), and l,3:2,4-di(3,4- dimethylbenzylidene) sorbitol (DMDBS), a calcium salt of dicarboxylic acid, a metal salt of cyclohexane dicarboxylic acid, a bisamide, a lithium carbonate, a benzoic acid, an inorganic oxide, nano-zinc oxide, talc, clay, powdered polymeric agents such as polyphenylene oxide, polyvinylenedifluoride, polycarbonate, polycarbonate- siloxane copolymer, cross-linked polycarbonate, polyetherimide, polyamide, ethylene propylene diene monomer, and polyoxymethylene.
15. The composition of claim 14, wherein: the clarifying and/or nucleating agent is present in an amount of 100 ppm to 200 ppm by total weight of the HDPE composition.
16. The composition of any of clai 14-15, wherein: the HDPE is at least one of a unimodal, bimodal, and multimodal HDPE.
17. The composition of any of cl aims 14-16, wherein: the HDPE has at least one of: an average molecular weight (Mw) of from 130,000 to 300,000 as determined by high temperature gel permeation chromatography; a poly dispersity index (PDI = Mw/Mn) of from 10 to 25 as determined by high temperature gel permeation chromatography; a melt flow rate (MFR) at 190 °C and 5 kg of from 0.5 g/10 min to 5 g/10 min as per ISO 1133; and a density of from 940 kg/m3 to 965 kg/m3 as per ASTM D1505.
18. The composition of any of cl aims 14-17, wherein: the HDPE composition is formed into an article of manufacture.
19. The composition of claim 18, wherein: the article is at least one of a film, a molded part, a container, a bottle, a beverage container cap, a lid, a sheet, a pipe, a pipe coupling, a bottle, a cup, a tray, a pallet, and a toy.
20. A method of forming a high-density polyethylene (HDPE) composition having increased transparency and/or reduced haze, the method comprising: modifying a HDPE by combining the HDPE with a monomeric and/or polymeric additive that is partially and/or fully dispersed within the HDPE, and a clarifying and/or nucleating agent in an amount of 100 ppm to 500 ppm by total weight of the HDPE composition so that the HDPE composition has at least one of a transparency of from 80% or more and a haze of from 60% or less as determined by ASTM D1003 at a thickness of from 1 mm or more.
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