WO2019229540A1 - Additif polymère permettant d'améliorer les propriétés de résistance à la fissuration sous contrainte environnementale de polymères - Google Patents

Additif polymère permettant d'améliorer les propriétés de résistance à la fissuration sous contrainte environnementale de polymères Download PDF

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WO2019229540A1
WO2019229540A1 PCT/IB2019/020010 IB2019020010W WO2019229540A1 WO 2019229540 A1 WO2019229540 A1 WO 2019229540A1 IB 2019020010 W IB2019020010 W IB 2019020010W WO 2019229540 A1 WO2019229540 A1 WO 2019229540A1
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Prior art keywords
polymer
polymer composition
composition
polymeric additive
article
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PCT/IB2019/020010
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English (en)
Inventor
Ana Paula Rodrigues Camilo
Barbara Iria Silva Mano
Marcelo FARAH
Marcos Roberto Paulino Bueno
Mariele Kaipers Stocker
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Braskem S.A.
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Priority to MX2020012489A priority Critical patent/MX2020012489A/es
Priority to BR112020024309-4A priority patent/BR112020024309A2/pt
Priority to TW108115103A priority patent/TW202003667A/zh
Priority to US16/502,673 priority patent/US11161945B2/en
Publication of WO2019229540A1 publication Critical patent/WO2019229540A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Definitions

  • Polyolefins such as polyethylene (PE) and polypropylene (PP) may be used to manufacture a varied range of articles, including films, molded products, foams, and the like.
  • Polyolefins may have characteristics such as high processability, low production cost, flexibility, low density and recycling possibility.
  • physical and chemical properties of polyolefin compositions may exhibit varied responses depending on a number of factors such as molecular weight, distribution of molecular weights, content and distribution of comonomer (or comonomers), method of processing, and the like.
  • Methods of manufacturing may utilize polyolefin’s limited inter- and intra- molecular interactions, capitalizing on the high degree of freedom in the polymer to form different microstructures, and to modify the polymer to provide varied uses in a number of technical markets.
  • polyolefin materials may have a number of limitations, which can restrict application such as susceptibility to deformation and degradation in the presence of some chemical agents, and low barrier properties to various gases and a number of volatile organic compounds (VOC).
  • Property limitations may hinder the use of polyolefin materials in the production of articles requiring low permeability to gases and solvents, such as packaging for food products, chemicals, household chemicals, agrochemicals, fuel tanks, water and gas pipes, and geomembranes, for example.
  • polyolefins While polyolefins are utilized in industrial applications because of favorable characteristics such as high processability, low production cost, flexibility, low density, and ease of recycling, polyolefin compositions may have physical limitations, such as susceptibility to environmental stress cracking (ESC) and accelerated slow crack growth (SCG), which may occur below the yield strength limit of the material when subjected to long-term mechanical stress. Polyolefin materials may also exhibit sensitivity to certain groups of chemical substances, which can lead to deformation and degradation. As a result, chemical sensitivities and physical limitations may limit the success in the replacement of other industry standard materials, such as steel and glass, with polyolefin materials because the material durability is insufficient to prevent chemical damage and spillage.
  • ESC environmental stress cracking
  • SCG accelerated slow crack growth
  • methods of altering the chemical nature of the polymer composition may include modifying the polymer synthesis technique or the inclusion of one or more comonomers.
  • modifying the polyolefin may also result in undesirable side effects.
  • increasing the molecular weight of a polyolefin may produce changes in the SCG and ESC, but can also increase viscosity, which may limit the processability and moldability of the polymer composition.
  • polyolefins may be copolymerized with alpha-olefins having a lower elastic modulus, which results in a considerable increase in environmental stress cracking resistance (ESCR) and resistance to impact but adversely affects the stiffness of the polymer.
  • ESCR environmental stress cracking resistance
  • alpha-olefins may have limited effectiveness because, while the incorporation of alpha-olefin comonomers must occur in the high molecular weight fraction in order to affect ESC and impact resistance, many popular catalyst systems have a low probability of inserting alpha-olefins in the high molecular weight fraction, an important factor in forming“tie molecules” between the chains of the surrounding polyolefin that are responsible for transferring stress between the crystalline regions and, consequently, responsible for important mechanical properties. The result is the production of a polymer composition having reduced structural stiffness.
  • Polymer modification by blending may vary the chemical nature of the composition, resulting in changes to the overall physical properties of the material.
  • Material changes introduced by polymer blending may be unpredictable, however, and, depending on the nature of the polymers and additives incorporated, the resulting changes may be uneven and some material attributes may be enhanced while others exhibit notable deficits.
  • the incorporation of a second phase into the matrix polymer which generally has a different chemical nature, may increase the resistance to impact and ESC resistance in some cases.
  • polymer blends are often accompanied by a marked loss in stiffness, because the blended materials may have lower elastic modulus than the matrix polyolefin.
  • embodiments disclosed herein relate to a polymer composition that includes a crosslinked polymeric additive composition that includes a matrix polymer comprising a polyolefin, and one or more polymer particles dispersed in the polymer matrix, wherein the one or more polymer particles comprise a polar polymer selectively crosslinked with a crosslinking agent; and a secondary polymer composition.
  • embodiments disclosed herein relate to a manufactured article that includes a polymer composition that includes a crosslinked polymeric additive composition that includes a matrix polymer comprising a polyolefin, and one or more polymer particles dispersed in the polymer matrix, wherein the one or more polymer particles comprise a polar polymer selectively crosslinked with a crosslinking agent; and a secondary polymer composition.
  • embodiments disclosed herein relate to a method that includes combining a crosslinked polymeric additive composition with a secondary polymer composition; wherein the crosslinked polymeric additive composition comprises a matrix polymer having a polar polymer internal phase that is selectively crosslinked with a crosslinking agent; and wherein combining the crosslinked polymeric additive composition with the secondary polymer compositions improves the environmental stress cracking resistance of the polymer composition with respect to the secondary polymer composition alone.
  • embodiments disclosed herein relate to a use of a crosslinked polymeric additive composition to improve the properties of a secondary polymer composition, the crosslinked polymeric additive composition comprising a matrix polymer having a polar polymer internal phase that is selectively crosslinked with a crosslinking agent.
  • Embodiments of the present disclosure are directed to polymer compositions that contained a crosslinked polymeric additive composition that may be used to improve the properties (including but not limited to environmental stress cracking resistance) of a secondary polymer composition.
  • the crosslinked polymeric additive composition may include a matrix polymer of a polyolefin and one or more polymer particles dispersed in the polymer matrix, where one or more polymer particles includes a polar polymer that is selectively crosslinked with a crosslinking agent.
  • the crosslinked polymeric additive composition may provide function to improve the properties of the secondary polymer composition to which the crosslinked polymeric additive composition is added.
  • the crosslinked polymer additive composition containing a mixture of polyolefin and polar polymer particles that may induce structural and/or morphological changes when compared to an unmodified polymer or blend, which may provide for the property improvement in the secondary polymer composition.
  • polymer compositions in accordance with the present disclosure may exhibit improvements in environmental stress cracking resistance, while also maintaining a balance of mechanical properties.
  • polymer compositions may be blended with a crosslinked polymeric additive to adjust various physical and chemical properties of the final composition.
  • physical and chemical properties of a polymer or polymer blend may be modified blending with a crosslinked polymeric additive incorporating a crosslinked polar polymer internal phase.
  • crosslinked polymer additives may also contain a functionalized polyolefin that may be added as a compatibilizing agent, in addition to other additives. Processes of manufacturing polymer compositions in accordance with the present disclosure may include various blending methods such a solution, emulsion, suspension, or extrusion.
  • Crosslinked polymeric additives in accordance with the present disclosure may be formulated as a“masterbatch” in which the polymer composition contains concentrations of polar polymer that are high relative to the polar polymer concentration in a final polymer blend for manufacture or use.
  • a masterbatch stock may be formulated for storage or transport and, when desired, be combined with additional polyolefin or other materials in order to produce a final polymer composition having concentration of constituent components that provides physical and chemical properties tailored to a selected end-use.
  • the polar polymer within the polymer composition may be crosslinked by a crosslinking agent to generate particulates containing intra-particle covalent linkages between the constituent polar polymer chains.
  • a crosslinking agent to generate particulates containing intra-particle covalent linkages between the constituent polar polymer chains.
  • inter-particle covalent linkages may also be formed.
  • the crosslinked polar polymer particles may create changes in the physical and physicochemical properties, including increases in ESCR and improvement in the balance of stiffness/impact resistance mechanical properties in relation to the properties of pure (unmodified or blended) polyolefins, as well as to secondary polymer compositions to which the crosslinked polymeric additive was added.
  • the balance of properties for modified polymer compositions may be expressed through a property balance index, which considers the combination of the flexural modulus, impact resistance and ESCR, discussed in more detail below.
  • the property balance index may be normalized against a reference polyolefin (without the polar polymer, etc.), and advantageously, the polymer compositions of the present disclosure may achieve a normalized property balance index that ranges from about 1.5 to 10, or greater than 1.5, or greater than 1.8, or from 3 to 6 in more particular embodiments.
  • polymer additives in accordance with the present disclosure may include a polymeric additive that may contain a polyolefin matrix polymer having an internal polar polymer phase that is crosslinked by a suitable crosslinking agent.
  • Crosslinked polymeric additives may be blended with various polymer types to modify a number of properties including stress cracking resistance, and the like.
  • Crosslinked polymeric additives in accordance with the present disclosure may include a matrix polymer component that surrounds other components in the composition, including polar polymer particles and other additives.
  • matrix polymers may include polyolefins produced from unsaturated monomers with the general chemical formula of C n H 2n -
  • polyolefins may include ethylene homopolymers, copolymers of ethylene and one or more C3-C20 alpha-olefins, propylene homopolymers, heterophasic propylene polymers, copolymers of propylene and one or more comonomers selected from ethylene and C4-C20 alpha-olefins, olefin terpolymers and higher order polymers, and blends obtained from the mixture of one or more of these polymers and/or copolymers.
  • matrix polymer may be selected from polyethylene with a density ranging from a lower limit selected from one of 0.890, 0.900, 0.910, 0.920, 0.930 and 0.940 g/cm 3 to an upper limit selected from one of 0.945, 0.950, 0.960 and 0.970 g/cm 3 measured according to ASTM D792, where any lower limit can be used with any upper limit; a melt index (I 2 ) ranging from a lower limit selected from one of 0.01, 0.1, 1, 10 and 50 g/lOmin to an upper limit selected from one of 10, 20, 50, 60, 100 and 200 g/10 min according to ASTM D1238 at 190°C/2.16 kg, where any lower limit can be used with any upper limit; and/or a melt index (I21) ranging from a lower limit selected from one of 0.1, 1, 3, 5, 10 and 50 g/lOmin to an upper limit selected from one of 10, 20, 30, 50, 100, 500, and 1000 g/10 min
  • the matrix polymer may include a high density polyethylene, with a density ranging from 0.930 g/cm 3 to 0.970 g/cm 3 according to ASTM D792 and a High Load Melt Index (HLMI) ranging from 1 to 60 g/10 min according to ASTM D 1238 at 190°C/21.6 kg.
  • HLMI High Load Melt Index
  • polymer compositions may contain a percent by weight of the total composition (wt%) of matrix polymer ranging from a lower limit selected from one of 30 wt%, 40 wt%, 50 wt%, 60 wt%, 75 wt%, and 85 wt%, to an upper limit selected from one of 60 wt%, 75 wt%, 80 wt%, 90 wt%, 95 wt%, 99.5 wt% and 99.9 wt%, where any lower limit can be used with any upper limit.
  • wt% percent by weight of the total composition (wt%) of matrix polymer ranging from a lower limit selected from one of 30 wt%, 40 wt%, 50 wt%, 60 wt%, 75 wt%, and 85 wt%, to an upper limit selected from one of 60 wt%, 75 wt%, 80 wt%, 90 wt%, 95 wt%, 99.5 wt% and 99.9
  • Polymer compositions in accordance with the present disclosure may include one or more polar polymers that are combined with a polyolefin and, further, may be crosslinked by one or more crosslinking agents.
  • a“polar polymer” is understood to mean any polymer containing hydroxyl, carboxylic acid, carboxylate, ester, ether, acetate, amide, amine, epoxy, imide, imine, sulfone, phosphone, and their derivatives, as functional groups, among others.
  • the polar polymer may be selectively crosslinked by an appropriate crosslinking agent, where the selective crosslinking may occur between the functional groups by reacting with a suitable crosslinking agent in the presence of polyolefins, additives, and other materials.
  • the crosslinking agent is selected to react with the polar polymer but without exhibiting reactivity (or having minimal reactivity towards) the polyolefin.
  • polar polymers include polyvinyl alcohol (PVOH), ethylene vinyl alcohol (EVOH) copolymer, ethylene vinyl acetate copolymer (EVA) and mixtures thereof.
  • polar polymers include polyvinyl alcohol.
  • One or more polar polymers in accordance with the present disclosure may be produced by hydrolyzing a polyvinyl ester to produce free hydroxyl groups on the polymer backbone.
  • polar polymers produced through hydrolysis may include polyvinyl alcohol generated from the hydrolysis of polyvinyl acetate.
  • the degree of hydrolysis for a polymer hydrolyzed to produce a polar polymer may be within the range of 30% and 100% in some embodiments, and between 70% and 99% in some embodiments.
  • Polar polymers in accordance with the present disclosure may have an intrinsic viscosity in the range of 2 mPa.s to 110 mPa.s in some embodiments, and between 4 mPa.s and 31 mPa.s in some embodiments. Intrinsic viscosity may be measured according to DIN 53015 using a 4 % aqueous solution at 20 °C. [0030] In one or more embodiments, polar polymer in accordance with the present disclosure may form a distinct phase within the polymer composition, which may be in the form of particles having an average particle size of less than 200 pm.
  • Particle size determinations may be made in some embodiments using SEM techniques after combination of polar polymer with the polyolefin by calculating relevant statistical data regarding particle size.
  • SEM imaging may be used to calculate particle size and develop size ranges using statistical analysis known for polymers and blends. Samples may be examined using SEM after hot pressing samples in accordance with ASTM D-4703 and polishing the internal part of the plate by cryo-ultramicrotomy. Samples may be dried and submitted to metallization with gold and imaged by FESEM (Field Emission Scanning Electron Microscopy, Model Inspect F50, from FEI), or by Tabletop SEM (Model TM-1000, from Hitachi).
  • FESEM Field Emission Scanning Electron Microscopy, Model Inspect F50, from FEI
  • Tabletop SEM Model TM-1000, from Hitachi
  • each crosslinked polar polymer particle may be measured from these images using the software such as LAS (version 43, from Leica). Calibration may be performed using the scale bar of each image and the measured values can be statistically analyzed by the software. The average value and standard deviation are given by the measurement of, at least, 300 particles.
  • Polar polymer particles in accordance with the present disclosure may have an average particle size having a lower limit selected from 0.01 mm, 0.5 mm, 1 mm, and 5 mm, and an upper limit selected from 10 mm, 20 mm, 30 mm, 50 mm, and 200 mm, where any lower limit may be used with any upper limit.
  • polymer compositions may contain a percent by weight of the total composition (wt%) of polar polymer ranging from a lower limit selected from one of 0.1 wt%, 0.25 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, and 25 wt%, to an upper limit selected from one of 5 wt%, 10 wt%, 15 wt%, 25 wt%, 50 wt%, 60 wt%, and 70 wt%, where any lower limit can be used with any upper limit.
  • wt% percent by weight of the total composition
  • compatibilizing agents such as functionalized polyolefins may be optionally added to modify the interactions between the polyolefin and the polar polymer.
  • “functionalized polyolefin” or compatibilizing agent is understood to mean any polyolefin which had its chemical composition altered by grafting or copolymerization, or other chemical process, using polar functionalizing reagents.
  • Functionalized polyolefins in accordance with the present disclosure include polyolefins functionalized with maleic anhydride, maleic acid, acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, methacrylate, acrylate, epoxy, silane, succinic acid, succinic anhydride, ionomers, and their derivatives, or any other polar comonomer, and mixtures thereof, produced in a reactor or by grafting.
  • polymer compositions may contain a percent by weight of the total composition (wt%) of functionalized polyolefin ranging from a lower limit selected from one of 0.1 wt%, 0.5 wt%, 1 wt%, and 5 wt%, to an upper limit selected from one of 5 wt%, 7.5 wt%, 10 wt%, and 15 wt%, where any lower limit can be used with any upper limit.
  • wt% percent by weight of the total composition (wt%) of functionalized polyolefin ranging from a lower limit selected from one of 0.1 wt%, 0.5 wt%, 1 wt%, and 5 wt%, to an upper limit selected from one of 5 wt%, 7.5 wt%, 10 wt%, and 15 wt%, where any lower limit can be used with any upper limit.
  • a crosslinking agent may be used to crosslink a selected polymer phase in a polymer composition.
  • a“crosslinking agent” is understood to mean any bi- or multi-functional chemical substance capable of reacting selectively with the polar groups of a polymer, forming crosslinks between and within the constituent polymer chains.
  • “selective” or“selectively” used alone or in conjunction with“crosslinking” or“crosslinked” is used to specify that the crosslinking agent reacts exclusively with the polar polymer, or that the crosslinking agent reacts with the polar polymer to a substantially greater degree (98% or greater, for example) than with respect to the polyolefin polymer.
  • Crosslinking agents in accordance with the present disclosure may react preferentially with a polar polymer, and may be non-reactive (or substantially non-reactive) with polyolefin.
  • the crosslinking agent is considered non-reactive (or not substantially reactive) to polyolefin when a composition consisting of the crosslinking agent and polyolefin may be processed with no changes or variations within a value of 2% (or lower) in rheology (complex viscosity), FTIR, and ESCR according to any applicable measurement method, as compared to a composition containing the polyolefin alone, according to any applicable measurement method provided the same method is applied to the comparative polyolefin and to the composition consisting of polyolefin and crosslinking agent.
  • crosslinking agents in accordance with the present disclosure may include linear, branched, saturated, and unsaturated carbon chains containing functional groups that react with counterpart functional groups present on the backbone and termini of a polar polymer incorporated into a polymer composition.
  • crosslinking agents may be added to a pre-mixed polymer blend containing a polyolefin and polar polymer particles, in order to crosslink the polar polymer in the presence of the polyolefin.
  • a crosslinking agent may react with the polar polymer within the particles, creating intraparticle crosslinks between the polar polymer chains.
  • Crosslinking agents in accordance with the present disclosure may include, for example, maleic anhydride, maleic acid, itaconic acid, itaconic anhydride, succinic acid, succinic anhydride, succinic aldehyde, adipic acid, adipic anhydride, phthalic anhydride, pthalic acid, citric acid, glutaconic acid, glutaconic anhydride, glutaraldehyde, sodium tetraborate, organic titanates such as tetrabutyl titanate, organic zirconates such as zirconium(IV) bis(diethyl citrato)dipropoxide, methoxy polyethylene glycol acrylates, ethoxy polyethylene glycol acrylates, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 1,3- butylene glycol diacrylate, 1,3-butylene glycol dimeth
  • crosslinking agents may be added to a blend used to form a polymer composition, such as the crosslinked polymeric additive, at a percent by weight (wt%) of the blend ranging from a lower limit selected from one of 0.001 wt%, 0.01 wt%, 0.05 wt%, 0.5 wt%, 1 wt%, and 2 wt% to an upper limit selected from one of 1.5 wt%, 2 wt%, 5 wt%, and 10 wt%, where any lower limit can be used with any upper limit.
  • wt% percent by weight
  • Polymer compositions in accordance with the present disclosure may include a mixture of crosslinked polymeric additive with a secondary polymer composition. While a number of exemplary polymer materials are described below it is envisioned that the secondary polymer composition may be any polymer suited for manufacturing applications. [0043] In one or more embodiments, the secondary polymer compositions may be selected from polyolefin, polystyrene, polyamide, polyester, ethylene vinyl alcohol, polyacrylate, polymethacrylate, poly(vinyl chloride), polycarbonate, polyssacharides, and rubber.
  • the secondary polymer compositions may be selected from polyethylene, polypropylene, polystyrene, poly(ethylene terephthalate), poly( vinyl chloride), polycarbonate, poly(methyl methacrylate) and polyamide. Further, it is also envisioned that any of the secondary polymers may be at least partially biobased.
  • the secondary polymer composition (including any of the above) may be a virgin polymer resin, while in others embodiments, the secondary polymer resin is a post-industrial polymer resin (PIR), a post-consumer polymer resin (PCR), a regrind polymer resin or combinations thereof.
  • PIRs, PCRs, regrind polymer resins, and combinations thereof may be present in a polymer composition in an amount higher than about 70 wt%, 80 wt%, 90 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt% or 99 wt%.
  • secondary polymer compositions may include homopolymers, copolymers, graft copolymers, and heterophasic polymers.
  • secondary polymer compositions may include acrylonitrile; butadiene-styrene (ABS); polyvinyl chloride (PVC); polyesters that include polylactic acid (PLA), polygly colic acid (PGA), poly-co- lactic-glycolic acid (PLGA), and the like; polyamides that include various nylons; polyacrylamide, polyacrylates, polymethacrylates; polyvinylalcohol (PVOH); polyolefins such as polypropylene polymers and copolymers; high melt strength polyolefins that include branched polyolefins and cross!
  • inked polyolefins polyolefin copolymers such as ethylene vinyl acetate (EVA); heterophasic polyolefins; polycarbonate (PC), polystyrene (PS); high impact polystyrene (HIPS), polycaprolactone (PCL); and the like.
  • EVA ethylene vinyl acetate
  • PC polycarbonate
  • PS polystyrene
  • HIPS high impact polystyrene
  • PCL polycaprolactone
  • secondary polymer may be selected from polyethylene with a density ranging from a lower limit selected from one of 0.890, 0.900, 0.910, 0.920, 0.930 and 0.940 g/cm 3 to an upper limit selected from one of 0.945, 0.950, 0.960 and 0.970 g/cm 3 measured according to ASTM D792, where any lower limit may be used in combination with any upper limit; a melt index (I 2 ) ranging from a lower limit selected from one of 0.01, 0.1, 1, 10 and 50 g/lOmin to an upper limit selected from one of 10, 20, 50, 100, and 200 g/lO min according to ASTM D1238 at l90°C/2.l6 kg, where any lower limit may be used in combination with any upper limit; and/or a melt index (I 2i ) ranging from a lower limit selected from one of 0.1, 1, 3.
  • the secondary polymer may include a high density polyethylene, with a density ranging from 0.930 g/cm 3 to 0.970 g/cm 3 according to ASTM D792 and a High Load Melt Index (HLMI) ranging from 1 to 60 g/10 min according to ASTM D 1238 at l90°C/2l.6 kg.
  • HLMI High Load Melt Index
  • the secondary polymer may be present in the polymer composition in an amount ranging from 5 to 99.9 wt% of the polymer composition, including having a lower limit of 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 wt% and an upper limit of 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or 99.9 wt%, where any lower limit can be used with any upper limit.
  • the polymer compositions of the present disclosure may contain a number of other functional additives that modify various properties of the composition such as antioxidants, pigments, fillers, reinforcements, adhesion-promoting agents, biocides, whitening agents, nucleating agents, anti-statics, anti-blocking agents, processing aids, flame-retardants, plasticizers, light stabilizers, and the like.
  • Polymer compositions in accordance with the present disclosure may include fillers and additives that modify various physical and chemical properties when added to the polymer composition during blending.
  • fillers and nanofillers may be added to a polymer composition to increase the barrier properties of the material by increasing the tortuous path of the polymer matrix for the passage of permeate molecules.
  • “nanofiller” is defined as any inorganic substance with at least a nanometric scale dimension.
  • Polymer composition in accordance with the present disclosure may be loaded with a filler and/or nanofiller that may include polyhedral oligomeric silsesquioxane (POSS), clays, nanoclays, silica particles, nanosilica, calcium nanocarbonate, metal oxide particles and nanoparticles, inorganic salt particles and nanoparticles, and mixtures thereof.
  • a filler and/or nanofiller may include polyhedral oligomeric silsesquioxane (POSS), clays, nanoclays, silica particles, nanosilica, calcium nanocarbonate, metal oxide particles and nanoparticles, inorganic salt particles and nanoparticles, and mixtures thereof.
  • fillers and/or nanofillers in accordance with the present disclosure may be incorporated into a polymer composition at a percent by weight (wt%) up to 70 wt%.
  • polymer compositions may contain a percent by weight of the total composition (wt%) of one or more additives ranging from a lower limit selected from one of 0.001 wt%, 0.01 wt%, 0.05 wt%, 0.5 wt%, and 1 wt%, to an upper limit selected from one of 1.5 wt%, 2 wt%, 5 wt%, and 7 wt%, where any lower limit can be used with any upper limit.
  • wt% percent by weight of the total composition
  • a masterbatch polymer composition may contain a percent by weight of the total composition (wt%) of crosslinked polar polymer ranging from a lower limit selected from one of 10 wt%, 20 wt% 25 wt%, 30 wt%, 40 wt%, and 50 wt% to an upper limit selected from one of 50 wt %, 60 wt%, and 70 wt%, where any lower limit can be used with any upper limit.
  • the crosslinked polymeric additive composition may be formulated as a masterbatch formulation that is combined with a secondary polymer composition to improve the properties of the secondary polymer composition, which may be a virgin polymer resin or a recycled material (including post industrial resins, post-consumer resins, and regrind polymer resin).
  • the masterbatch formulation may be used to improve the properties of the secondary polymer composition in order to recover or restore (at least partially or wholly) the properties of the secondary polymer composition to its original level (i.e., to a level that is close to or substantially the same as a virgin resin thereof) or higher than the original level.
  • the polymer composition contains concentrations of polar polymer that are high relative to the polar polymer concentration in a final polymer blend for manufacture or use.
  • the masterbatch composition may be combined with an additional quantity of secondary polymer to arrive at a polar polymer concentration in the final composition that is lower than the masterbatch concentration.
  • the crosslinked polymeric additive composition may be present in the final polymer composition (combined with the secondary polymer composition) at a percent by weight of the polymer composition that ranges from 0.01 wt% to 95 wt%, where the lower limit may include any of 0.01, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 wt%, and the upper limit includes any of 50, 55, 60, 65, 70 75, 80, 85, 90, or 95 wt%, where any lower limit can be used in combination with any upper limit.
  • Polymer compositions in accordance with the present disclosure may be prepared by a number of possible polymer blending and formulation techniques, which will be discussed in the following sections.
  • a crosslinked polymeric additive composition may be combined with a secondary polymer composition; wherein combining the crosslinked polymeric additive composition with the secondary polymer compositions improves the environmental stress cracking resistance of the polymer composition with respect to the secondary polymer composition alone.
  • the crosslinked polymeric additive composition is combined with a secondary polymer composition in a melt blend process. In one or more other embodiments, the crosslinked polymeric additive composition is combined with a secondary polymer composition in a dry blend process.
  • the crosslinked polymeric additive may be formulated as a masterbatch formulation that may be diluted in a subsequent melt-blend or dry blend process to form the final polymer composition having the improved properties.
  • the crosslinked polymeric additive composition may be initially formed, such as in a reactive extrusion process or the like to form the selectively crosslinked polymer particles within the matrix polymer.
  • Such crosslinked polymeric additive composition may subsequently be combined with a secondary polymer composition, may be subjected to a conventional extrusion process (melt-blending), for example, to blend the polymers together, thereby forming an improved secondary polymer or it may be mixed manually or in a dry-mixer or even added directly together with the secondary polymer (dry blending) into the hopper of the plastic manufacturing machine, such as a blowmolding or a injection molding machine.
  • a conventional extrusion process for example, to blend the polymers together, thereby forming an improved secondary polymer or it may be mixed manually or in a dry-mixer or even added directly together with the secondary polymer (dry blending) into the hopper of the plastic manufacturing machine, such as a blowmolding or a injection molding machine.
  • crosslinked polymeric additive compositions in accordance with the present disclosure may be prepared using continuous or discontinuous extrusion.
  • Methods may use single-, twin- or multi-screw extruders, which may be used at temperatures ranging from 100 °C to 270 °C in some embodiments, and from 140 °C to 230 °C in some embodiments.
  • raw materials are added to an extruder, simultaneously or sequentially, into the main or secondary feeders in the form of powder, granules, flakes or dispersion in liquids as solutions, emulsions and suspensions of one or more components.
  • the components can be pre-dispersed in prior processes using intensive mixers, for example. Inside an extrusion equipment, the components are heated by heat exchange and/or mechanical friction, the phases are melt and the dispersion occurs by the deformation of the polymer.
  • one or more compatibilizing agents such as a functionalized polyolefin
  • the crosslinking agent can be added at the same extrusion stage or in a consecutive extrusion, according to selectivity and reactivity of the system.
  • methods of preparing polymer compositions may involve a single extrusion or multiple extrusions following the sequences of the blend preparation stages. Blending and extrusion also involve the selective crosslinking of the polar polymer in the dispersed phase of the polymer composition by the crosslinking agent.
  • Extrusion techniques in accordance with the present disclosure may also involve the preparation of a polar polymer concentrate (a masterbatch), combined with a crosslinking agent in some embodiments, that is then combined with other components to produce a polymer composition of the present disclosure.
  • a polar polymer concentrate a masterbatch
  • the morphology of a crosslinked polar polymer may be stabilized by crosslinking when dispersed in a polymer matrix containing polyolefins and is not dependent on subsequent processes for defining the morphology.
  • Polymer compositions prepared by melt-blending or dry-blending may be in the form of granules that are applicable to different molding processes, including processes selected from extrusion molding, injection molding, thermoforming, cast film extrusion, blown film extrusion, foaming, extrusion blow-molding, ISBM (Injection Stretched Blow-Molding), rotomolding, pultrusion, additive manufacturing, lamination, and the like, to produce manufactured articles.
  • molding processes including processes selected from extrusion molding, injection molding, thermoforming, cast film extrusion, blown film extrusion, foaming, extrusion blow-molding, ISBM (Injection Stretched Blow-Molding), rotomolding, pultrusion, additive manufacturing, lamination, and the like, to produce manufactured articles.
  • the article is an injection molded article, a thermoformed article, a film, a foam, a blow molded article, a 3D printed article, a compressed article, a coextruded article, a laminated article, an injection blow molded article, a rotomolded article, an extruded article, or a pultruded article.
  • polymer compositions may be used in the manufacturing of articles, including rigid and flexible packaging for food products, household chemicals, chemicals, agrochemicals, fuel tanks, water and gas pipes, geomembranes, recycled articles, and the like.
  • sample formulations were compression molded in 2 mm thick plaques according to ASTM D-4703, at 200°C and under pressure. Samples were notched, bent to achieve deformation and placed in a metal U-shaped specimen holder, and placed in an aqueous solution containing nonylphenol ethoxylate (IGEPALTM CO-630 from Solvay) at a percent by volume (vol%) of 10 vol%. Failure was determined as the appearance of any crack visible by the naked eye, in accordance with ASTM D-1693 procedure B.
  • IGEPALTM CO-630 nonylphenol ethoxylate
  • the IZOD impact resistance at 23°C of the material was determined according to ASTM D-256. Samples were previously compression molded in plaques in accordance with ASTM D4703.
  • PBI values were normalized according to Eq. 2, where NPBI is the normalized property balance index, PBI sample is the property balance index obtained for the samples of polymer composition including the crosslinked polymeric additive and the secondary polymer and PBI reference is the property balance index obtained for the reference samples, i.e., a polymer composition comprising the secondary polymer without the crosslinked polymeric additive.
  • Polymer compositions in accordance with the present disclosure may exhibit an N PBI higher than about 1.0 or higher than about one of 1.5, 2.0, 3.0, 5.0 and 10. In another embodiment, polymer compositions in accordance with the present disclosure may exhibit an N PBI falling within the range of 1.5 to 10 in some embodiments, and within the range of 3 to 9 in some embodiments. Polymer compositions in accordance with the present disclosure may exhibit an NPBI that is at least 1.5 in other embodiments. In some embodiments, the NPBI value is greater than 1.8.
  • a crosslinked polymeric additive was formulated as a masterbatch composition, containing 50 wt% of polyethylene as a matrix polymer and 50 wt% of selectively crosslinked PVOH based in the masterbatch composition, which was combined with high density polyethylene (HDPE) to final contents of 3, 4 and 5 wt% of selectively crosslinked PVOH and processed in ZSK26 twin screw extruder or extrusion blow molding equipment. Trials with different polyethylene (PE) resin were performed to observe the final product properties. Four different methods of combination with the HDPE resin were used. The additives used are primary and secondary antioxidants commonly used for HDPE resins.
  • HDPE high density polyethylene
  • Method A Neat HDPE with antioxidants additivation in extrusion, named as additivated HDPE (extrusion - ZSK26 twin screw)
  • Method B Melt-blend of the crosslinked polymer additive masterbatch with neat HDPE and antioxidants additives in extrusion (extrusion - ZSK26 twin screw)
  • Method C Melt-blend of the masterbatch of the crosslinked polymer additive with additivated HDPE (prepared by Method A) (extrusion - ZSK26 twin screw)
  • Method D Blow-molding of additivated HDPE (prepared by Method A) without masterbatch.
  • Method E Blow molding of dry-blend of masterbatch with additivated HDPE (prepared by Method A) in the blow-molding machine’s hopper and posterior blow-molding
  • the resins used in combination (secondary polymer composition) with the masterbatch composition (to improve the properties of the resins) include those shown in Table 1 below:
  • Resin 1, Resin 2, and Resin 3 showed increase in ESCR results and NPBI (Table 2) according to the raising in the concentration of crosslinked PVOH (and consequently in the added masterbatch) (3% 5%) added in HDPE resin.
  • the crosslinked polymeric additive (referred herein as MB) as formulated previously was added in post-consumer resins obtained from WISEWOOD COMPANY, BRAZIL, from small volume blown bottles of domestic trash.
  • the crosslinking polymeric additive as described above was combined with PCR to final contents of 1, 3, 5 and 7 wt% of selectively crosslinked PVOH and processed in ZSK26 twin screw extruder or extrusion blow molding equipment.
  • Table 5 presents the results of the mechanical tests and NPBI results obtained for the samples formulated with the post-consumer resins.
  • inventive composition increases the ESCR results maintaining and sometimes even increasing the impact resistance and flexural modulus of the base resin.
  • the inventive polymer composition as described in the present disclosure is a reliable solution for the recycling of polymers, as normally those resins, due to the use and degradation suffered in the plastic production value chain, have a significant decrease in its ESCR, making it impossible to be used in noble applications that requires this property. It is also clear that even for compositions with very high PCR concentration (such as 99 wt%), the ESCR property achieved is similar to a virgin resin (GF4950).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de polymère qui peut comprendre une composition d'additif polymère réticulé qui comprend un polymère matriciel comprenant une polyoléfine, et une ou plusieurs particules polymères dispersées dans la matrice polymère, lesdites une ou plusieurs particules polymères comprenant un polymère polaire réticulé sélectivement avec un agent de réticulation ; et une composition de polymère secondaire.
PCT/IB2019/020010 2015-10-01 2019-04-19 Additif polymère permettant d'améliorer les propriétés de résistance à la fissuration sous contrainte environnementale de polymères WO2019229540A1 (fr)

Priority Applications (4)

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MX2020012489A MX2020012489A (es) 2018-05-31 2019-04-19 Aditivo polimérico para mejorar las propiedades de resistencia al agrietamiento por estrés ambiental de polímeros.
BR112020024309-4A BR112020024309A2 (pt) 2018-05-31 2019-04-19 composição de polímero, artigo fabricado, método, e, uso de uma composição de aditivo polimérico reticulado
TW108115103A TW202003667A (zh) 2018-05-31 2019-04-30 用於改良聚合物之抗環境應力龜裂性質的聚合性添加劑
US16/502,673 US11161945B2 (en) 2015-10-01 2019-07-03 Polymeric additive for improving polymer environmental stress cracking resistance properties

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US62/678,816 2018-05-31

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2223965A1 (fr) * 2007-12-20 2010-09-01 Kuraray Co., Ltd. Composition polymère thermoplastique et article moulé à base de cette composition
US20170096552A1 (en) * 2015-10-01 2017-04-06 Braskem S.A. Polyolefin compositions with improved mechanical and barrier properties

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2223965A1 (fr) * 2007-12-20 2010-09-01 Kuraray Co., Ltd. Composition polymère thermoplastique et article moulé à base de cette composition
US20170096552A1 (en) * 2015-10-01 2017-04-06 Braskem S.A. Polyolefin compositions with improved mechanical and barrier properties

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