EP3880752A1 - Compositions contenant de l'eva présentant des propriétés mécaniques améliorées et articles et procédés associés - Google Patents

Compositions contenant de l'eva présentant des propriétés mécaniques améliorées et articles et procédés associés

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Publication number
EP3880752A1
EP3880752A1 EP19823990.7A EP19823990A EP3880752A1 EP 3880752 A1 EP3880752 A1 EP 3880752A1 EP 19823990 A EP19823990 A EP 19823990A EP 3880752 A1 EP3880752 A1 EP 3880752A1
Authority
EP
European Patent Office
Prior art keywords
polymer composition
composition
astm
eva
ranges
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP19823990.7A
Other languages
German (de)
English (en)
Inventor
Giancarlos DELEVATI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Braskem SA
Original Assignee
Braskem SA
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 Braskem SA filed Critical Braskem SA
Publication of EP3880752A1 publication Critical patent/EP3880752A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • compositions are used to produce a varied range of articles for many different applications.
  • Such compositions may be formulated with a variety of rubbers and other additives to provide articles that possess physical properties well-suited for their intended use.
  • articles that are intended to be for the automotive market may possess, among others, enhanced physical and chemical properties that resemble those of traditional thermoplastic elastomer materials used in the industry.
  • Blends or alloys of plastic and elastomeric rubber have been historically relevant in the production of high performance thermoplastic elastomers, particularly for the replacement of thermoset rubber in various applications.
  • Polyolefin copolymers such as ethylene vinyl acetate (EVA) may be used to manufacture a varied range of articles, including films, molded products, foams, and the like.
  • EVA ethylene vinyl acetate
  • polyolefins are widely used plastics worldwide, given their versatility in a wide range of applications. While EVA may have characteristics such as high process-ability, low production cost, flexibility, low density and recycling possibility, physical and chemical properties such as tackiness and deformability may create difficulties during processing and 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.
  • thermoplastic polymer compositions derived from ethylene vinyl acetate (EVA) copolymers include thermoplastic polymer compositions derived from ethylene vinyl acetate (EVA) copolymers.
  • EVA compositions particularly those of low to medium vinyl acetate content, have not been heavily utilized for the manufacture of articles for the automotive industry. This is generally because such compositions tend to have a low hardness compared to the hardness required for use in such applications.
  • Polymer compositions containing EVA can be thermoplastic in nature, and so they can be easily formed into articles.
  • embodiments disclosed herein relate to polymer compositions that include an elastomeric EVA composition in an amount ranging from about 46 to 70 wt% of the polymer composition; and a polypropylene in an amount ranging from about 20 to 40 wt% of the polymer composition.
  • embodiments disclosed herein relate to polymer compositions that include an elastomeric EVA composition; and a polypropylene, where the polymer composition has a Shore D Hardness according to ASTM D2240 that ranges from 25 to 54 Shore D; and a tensile modulus at 100% elongation according to ASTM D638 that ranges from 5 to 20 MPa.
  • thermoplastic article that includes a polymer composition that include an elastomeric EVA composition in an amount ranging from about 46 to 70 wt% of the polymer composition; and a polypropylene in an amount ranging from about 20 to 40 wt% of the polymer composition.
  • thermoplastic article that includes a polymer composition that include an elastomeric EVA composition; and a polypropylene, where the polymer composition has a Shore D Hardness according to ASTM D2240 that ranges from 25 to 54 Shore D; and a tensile modulus at 100% elongation according to ASTM D638 that ranges from 5 to 20 MPa.
  • embodiments disclosed herein relate to methods that include mixing an elastomeric EVA composition with polypropylene, and extruding the mixture of elastomeric EVA composition and polypropylene. [0010] In yet another aspect, embodiments disclosed herein relate to molding a polymer composition that include an elastomeric EVA composition in an amount ranging from about 46 to 70 wt% of the polymer composition; and a polypropylene in an amount ranging from about 20 to 40 wt% of the polymer composition, to form an article.
  • embodiments disclosed herein relate to molding a polymer composition that include an elastomeric EVA composition; and a polypropylene, where the polymer composition has a Shore D Hardness according to ASTM D2240 that ranges from 25 to 54 Shore D; and a tensile modulus at 100% elongation according to ASTM D638 that ranges from 5 to 20 MPa, to form an article.
  • Embodiments of the present disclosure are directed to the production of thermoplastic blended compositions that exhibit desired mechanical and chemical properties that include, but are not limited to, increased hardness, modified stiffness and tensile modulus, and enhanced thermal and chemical stability.
  • embodiments of the present disclosure are directed to methods of the manufacture of blended polymer compositions, including blends containing elastomeric ethylene vinyl acetate (EVA) resin and a polypropylene, and articles thereof with enhanced mechanical properties.
  • EVA elastomeric ethylene vinyl acetate
  • Embodiments disclosed herein generally relate to compounded thermoplastic polymer compositions containing ethylene vinyl acetate (EVA) copolymers.
  • EVA ethylene vinyl acetate
  • One or more embodiments disclosed herein relate to polymer compositions that comprise EVA, and polypropylene.
  • polymer compositions of the present disclosure may be used to form articles comprising EVA copolymer and polypropylene.
  • EVA-derived materials do not exhibit the requisite physical properties, such as hardness, and chemical stability that would provide for its use in applications such as those found in the automotive market.
  • the thermoplastic EVA compounded compositions, and articles therefrom, of one or more embodiments of the present disclosure possess superior properties to traditional materials.
  • Such articles may possess thermoplastic and elastomeric properties, including increased hardness with appropriate tensile modulus and improved chemical properties for enhanced performance of articles thereof.
  • Some embodiments are especially suited for use in high performance aerodynamic deflectors and air dams, in the automotive industry.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may be generated in post-reactor processes.
  • Polymer compositions may be prepared from a polypropylene with an elastomeric EVA composition in a post reactor melt mixture process, including extruders and intensive mixers.
  • each component isolated may be combined in controlled stoichiometry to generate polymer composition while minimizing the presence of reactants and degradation products.
  • a subset of the components may be combined by melt mixing followed by subsequent mixing steps, or all components may be melt mixed simultaneously.
  • embodiments of the present disclosure are directed to polymer compositions containing polypropylene and an elastomeric EVA composition.
  • Polymer compositions in accordance with the present disclosure may include polypropylene.
  • polypropylene may include propylene homopolymers, heterophasic propylene polymers, copolymers of propylene and one or more comonomers selected from ethylene and C4-C20 alpha-olefins, propylene terpolymers and higher order polymers, and blends obtained from the mixture of one or more of these polymers and/or copolymers.
  • polypropylene may be generated with a suitable catalyst such as Ziegler-Natta and metallocene catalysts.
  • polymer compositions may include biobased and recycled polypropylene produced from propylene monomers, including polypropylene of varying molecular weight and density, and blends and mixtures thereof.
  • polymer compositions may include polypropylene homopolymers and/or polypropylene copolymers or mixtures thereof.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may include a polypropylene at a percent by weight of the composition that ranges from a lower limit of about 20 wt% to an upper limit of about 40 wt%.
  • the lower limit may range from 20, 22, 24, 26, 28, or 30 wt%
  • the upper limit may range from 30, 32, 34, 36, 38, 40 wt%, where any lower limit may be used in combination with any upper limit.
  • Polymer compositions may be formulated with polypropylene in specific to provide articles produced therefrom with the requisite physical properties for their intended use.
  • articles that are intended to be for the automotive market may exhibit, among others, the following characteristics: adequate hardness, impact strength, flexibility, tensile modulus, and additionally for specific applications, improved chemical properties.
  • thermoplastic EVA compounded compositions may be formulated with polypropylene wherein the polypropylene may have a melt flow index (MFI) at 230 °C and 2.16 kg as determined according to ASTM D1238 in a range having a lower limit of at least 3 g/lOmin, to an upper of at most 45g/10min.
  • MFI melt flow index
  • polypropylene that may have a melt flow index (MFI) at 230 °C and 2.16 kg as determined according to ASTM D1238 in a range having a lower limit of at least 4 g/lOmin, to an upper of at most 40g/10min.
  • Biobased polypropylenes in accordance with the present disclosure may include polyolefins containing a weight percentage of biologically derived monomers.
  • Propylene monomers may be derived from similar biological processes as discussed, for example, in U.S. Pat. Pub. 2013/0095542.
  • biologically derived n-propanol may be dehydrated to yield propylene, which is then polymerized to produce various types of polypropylene.
  • Biobased polypropylene in accordance with the present disclosure may include a homopolymer, random copolymer, heterophasic copolymer or terpolymer, and the like.
  • Biobased polypropylenes in accordance with the present disclosure may include a polypropylene having a biobased content at a percent by weight (wt%) in a range having a lower limit selected from any of 0.05 wt%, 0.1 wt%, 1 wt%, and 5 wt%, to an upper limit selected from any of 50%, 90%, and 100%, where any lower limit may be combined with any upper limit.
  • wt% percent by weight
  • biobased products obtained from natural materials may be certified as to their renewable carbon content, according to the methodology described in the technical standard ASTM D 6866-06,“Standard Test Methods for Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis.”
  • Thermoplastic EVA compounded composition in accordance with the present disclosure may include recycled polypropylenes obtained from various sources including post-industrial resins, post-consumer resins, regrind polymer resins, and combinations thereof.
  • recycled polypropylene may be obtained by a general process of selecting a polypropylene from a polypropylene waste residue, cleaning the polypropylene, and processing the polypropylene to generate polypropylene flakes.
  • processing to generate polypropylene flakes may occur before the cleaning step.
  • the recycling process further comprises the step of extruding the polypropylene flakes to generate polypropylene pellets.
  • Thermoplastic EVA compounded compositions in accordance to the present disclosure may include an elastomeric ethylene vinyl acetate (EVA) compositions prepared from (A) EVA copolymer, (B) ethylene alpha-olefin copolymer, (C) polyorganosiloxane, (D) plasticizer, and (E) rubber.
  • EVA elastomeric ethylene vinyl acetate
  • EVA compositions are prepared as disclosed in the Brazilian patent BR 102012025160-4, incorporated herein by reference in its entirety.
  • the major components of the elastomeric EVA composition of the present disclosure as well as their respective properties are detailed below.
  • elastomeric EVA compositions may be VA4018R, SVT2145R, VA1518A, VA2510A, VA5018ALS or any other resin under the EVANCETM, and combinations thereof, which are commercially available by Braskem.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may include an elastomeric EVA at a percent by weight of the composition that ranges from a lower limit selected from a lower limit of about 40 wt% to an upper limit of about 70 wt% of the thermoplastic EVA compounded composition.
  • the lower limit may range from 40, 42, 44, 46, 48, 50, or 55 wt%
  • the upper limit may range from 60, 62, 64, 66, 68, 70wt%, where any lower limit may be used in combination with any upper limit.
  • Elastomeric EVA compositions of the present invention may incorporate one or more ethylene-vinyl acetate (EVA) copolymers prepared by the copolymerization of ethylene and vinyl acetate.
  • EVA copolymer can be derived from petroleum or renewable sources (such as biobased EVA).
  • Biobased EVA is an EVA wherein at least one of ethylene and/or vinyl acetate monomers are derived from renewable sources, such as ethylene derived from biobased ethanol.
  • EVA copolymers in accordance with the present disclosure may include a percent by weight (wt%) of vinyl acetate according to ASTM D5594 that ranges from a lower limit of about 2 wt% to an upper limit of about 50 wt% of the EVA copolymer.
  • the amount of vinyl acetate may be of the range 5-40 wt% of the EVA copolymer.
  • the lower limit may range from 2, 5, 8, 10, 12, 15, or 20 wt%
  • the upper limit may range from 20, 25, 30, 35, 40, 45 or 50 wt% of the EVA copolymer, where any lower limit may be used in combination with any upper limit.
  • EVA copolymers in accordance with the present disclosure may include a percent by weight of ethylene that ranges from a lower limit of about 50 wt% to an upper limit of about 98 wt% of the EVA copolymer.
  • Elastomeric EVA compositions in accordance with the present disclosure may contain an EVA copolymer at a percent by weight (wt%) of the elastomeric EVA composition that ranges from a lower limit of 20 wt%, 30wt%, 40 wt% or 50 wt%, to an upper limit of 60 wt%, 70 wt%, 80 wt% or 90 wt%, where any lower limit may be paired with any upper limit.
  • wt% percent by weight
  • Elastomeric EVA compositions in accordance with the present disclosure may incorporate one or more ethylene alpha-olefin copolymers prepared from the polymerization of ethylene and one or more of a C3 to C20 alpha-olefin.
  • Ethylene alpha-olefin copolymer in accordance with the present disclosure may have a hardness determined in accordance with ASTM D2240 in a range having a lower limit selected from any of 10 Shore A, 15 Shore A, and 20 Shore A, to an upper limit selected from any of 70 Shore A, 75 Shore A, and 80 Shore A, where any lower limit may be paired with any upper limit.
  • Ethylene alpha-olefin copolymer in accordance with the present disclosure may have a density determined according to ASTM D792 in a range having a lower limit selected from any of 0.80 g/cm3, 0.85 g/cm3, and 0.88 g/cm3, to an upper limit selected from any of 0.89 g/cm3, 0.90 g/cm3, and 0.95 g/cm3, where any lower limit may be paired with any upper limit.
  • Ethylene alpha-olefin copolymer in accordance with the present disclosure may have a melt flow index (MFI) at 190 °C and 2.16 kg as determined according to ASTM D1238 in a range having a lower limit selected from any of 0.01 g/lOmin, 0.05 g/lOmin, and 0.1 g/lOmin, to an upper limit selected from any of 70 g/lOmin, 75 g/lOmin, and 100 g/lOmin, where any lower limit may be paired with any upper limit.
  • MFI melt flow index
  • Elastomeric EVA compositions in accordance with the present disclosure may contain an ethylene alpha-olefin copolymer at a percent by weight (wt%) of the composition that ranges from a lower limit of 5 wt% or 10 wt%, to an upper limit of 30 wt% or 60 wt%, where any lower limit may be paired with any upper limit.
  • wt% percent by weight
  • Elastomeric EVA compositions in accordance with the present disclosure may incorporate a polyorganosiloxane.
  • suitable polyorganosiloxanes include a linear chain, branched, or three-dimensional structure, wherein the side groups can include one or more of methyl, ethyl, propyl groups, vinyl, phenyl, hydrogen, amino, epoxy, or halogen substituents.
  • the terminal groups of the polyorganosiloxane may include hydroxyl groups, alkoxy groups, trimethylsilyl, dimethyldiphenylsilyl, and the like.
  • Polyorganosiloxanes in accordance with the present disclosure may include one or more of dimethylpolysiloxane, methylpolysiloxane, and the like.
  • Elastomeric EVA compositions in accordance with the present disclosure may contain a polyorganosiloxane having a viscosity measured at 25° C according to ASTM D4287 that ranges from a lower limit of 20 cP or 40 cP, to an upper limit of 700,000 cP or 900,000 cP, where any lower limit may be paired with any upper limit.
  • Elastomeric EVA compositions in accordance with the present disclosure may contain a polyorganosiloxane at a percent by weight (wt%) of the elastomeric EVA composition that ranges from a lower limit of 0.1 wt% or 0.5 wt%, to an upper limit of 5 wt% or 10 wt%, where any lower limit may be paired with any upper limit
  • Elastomeric EVA compositions in accordance with the present disclosure may incorporate a plasticizer to improve the process-ability and adjust the hardness of the elastomeric EVA composition.
  • Plasticizers in accordance with the present disclosure may include one or more of bis(2-ethylhexyl) phthalate (DEHP), di-isononyl phthalate (DINP), bis (n-butyl) phthalate (DNBP), butyl benzyl phthalate (BZP), di- isodecyl phthalate (DIDP), di-n-octyl phthalate (DOP or DNOP), di-o-octyl phthalate (DIOP), diethyl phthalate (DEP), di-isobutyl phthalate (DIBP), di-n-hexyl phthalate, tri-methyl tri meditate (TMTM), tri-(2-ethylhexyl) trimellitate (TEHTM-MG), tri-(n-(
  • Elastomeric EVA compositions in accordance with the present disclosure may contain a plasticizer at a percent by weight (wt%) of the composition that ranges from a lower limit of 0.5 wt% or 2 wt%, to an upper limit of 10 wt% or 20 wt%, where any lower limit may be paired with any upper limit.
  • wt% percent by weight
  • Elastomeric EVA compositions in accordance with the present disclosure may incorporate a rubber component to increase the rubbery touch and increase the coefficient of friction, depending on the end application.
  • Rubbers in accordance with the present disclosure may include one or more of natural rubber, poly-isoprene (IR), styrene and butadiene rubber (SBR), polybutadiene, nitrile rubber (NBR); polyolefin rubbers such as ethylene -propylene rubbers (EPDM, EPM), and the like, acrylic rubbers, halogen rubbers such as halogenated butyl rubbers including brominated butyl rubber and chlorinated butyl rubber, brominated isotubylene, polychloroprene, and the like; silicone rubbers such as methyl vinyl silicone rubber, dimethyl silicone rubber, and the like, sulfur-containing rubbers such as polysulfidic rubber; fluorinated rubbers; thermoplastic rubbers such as elastomers based on styrene, buta
  • Rubbers in accordance with the present disclosure may have a hardness determined in accordance with ASTM D2240 in a range having a lower limit selected from any of 10 Shore A, 15 Shore A, and 20 Shore A, to an upper limit selected from any of 45 Shore A, 50 Shore A, and 55 Shore A, where any lower limit may be paired with any upper limit.
  • Elastomeric EVA compositions in accordance with the present disclosure may contain a rubber at a percent by weight (wt%) of the composition that ranges from a lower limit of 0.5 wt% or 1 wt%, to an upper limit of 20 wt% or 40 wt%, where any lower limit may be paired with any upper limit.
  • wt% percent by weight
  • thermoplastic EVA compounded compositions in accordance with the present disclosure may include Elastomeric EVA compositions prepared as described above, and polypropylene, along with additives such as fillers, antioxidants, slip agents, carbon black, anti-uv additives, and plasticizers.
  • the thermoplastic EVA compounded compositions of the present disclosure may contain a number of other functional additives that modify various properties of the composition when added to the polymer composition during blending that include one or more polymer additives such as antioxidants, anti-UV additives, pigments, fillers, reinforcements, adhesion- promoting agents, biocides, whitening agents, nucleating agents, slip agents such as zinc stearate, anti-statics, anti-blocking agents, processing aids, flame-retardants, plasticizers, light stabilizers, and the like.
  • polymer additives such as antioxidants, anti-UV additives, pigments, fillers, reinforcements, adhesion- promoting agents, biocides, whitening agents, nucleating agents, slip agents such as zinc stearate, anti-statics, anti-blocking agents, processing aids, flame-retardants, plasticizers, light stabilizers, and the like.
  • thermoplastic EVA compounded compositions may contain a percent by weight of the total composition (wt%) of one or more additives, listed above, ranging from a lower limit of 0.1 wt% to and upper limit of 15 wt%.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may include anti-UV additives such as benzophenones, benzotriazoles, hindered amines, or carbon black.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may include a percent by weight of the total composition (wt%) of an anti-UV additive ranging from a lower limit of 0.5, 1, 1.5 wt% to an upper limit of 2.5, 3, 3.5 wt% or 10wt%, where any lower limit may be combined with any upper limit.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may include one or more antioxidants such as phenolic and phosphitic antioxidants.
  • Thermoplastic EVA compounded compositions in accordance with one or more embodiments of the present disclosure may include an antioxidant at a percent by weight (wt%) of the composition that ranges from a lower limit of 0.1 wt% or 0.15 wt%, to an upper limit of 0.25 wt% or 0.3 wt%, where any lower limit may be paired with any upper limit.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may include one or more slip agents including long chain fatty acid amides or metal salts of a fatty acid such as metallic stearates (including zinc stearate and calcium stearate, for example) to provide for improved performance at higher temperatures, improved reliability and reduced coefficient of friction.
  • slip agents including long chain fatty acid amides or metal salts of a fatty acid such as metallic stearates (including zinc stearate and calcium stearate, for example) to provide for improved performance at higher temperatures, improved reliability and reduced coefficient of friction.
  • Thermoplastic EVA compounded compositions in accordance with one or more embodiments of the present disclosure may include a slip agent at a percent by weight (wt%) of the composition that ranges from a lower limit of 0.05 wt%, 0.1 wt%, or 0.15 wt% to an upper limit of 0.75 wt%, 0.8 wt%, 0.85 wt% and 1 wt% where any lower limit may be paired with any upper limit.
  • wt% percent by weight
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may include one or more inorganic fillers such as talc, glass fibers, marble dust, cement dust, clay, carbon black, feldspar, silica or glass, fumed silica, silicates, calcium silicate, silicic acid powder, glass microspheres, mica, metal oxide particles and nanoparticles such as magnesium oxide, antimony oxide, zinc oxide, inorganic salt particles and nanoparticles such as barium sulfate, wollastonite, alumina, aluminum silicate, titanium oxides, calcium carbonate, polyhedral oligomeric silsesquioxane (POSS).
  • inorganic fillers such as talc, glass fibers, marble dust, cement dust, clay, carbon black, feldspar, silica or glass, fumed silica, silicates, calcium silicate, silicic acid powder, glass microspheres, mica, metal oxide particles and nanoparticles such as magnesium oxide, antimony oxide, zinc
  • thermoplastic EVA compounded compositions may contain an amount of filler ranging from a lower limit of any of 5, 6, or 8 wt% to an upper limit of any of 8, 10, or 12 wt%, where any lower limit may be used in combination with any upper limit.
  • a component such as carbon black may be selected for use as both a filler and an anti-UV agent. If a different filler is used that does not have the same anti-UV effect as carbon black, it is understood that it also may be desirable to incorporate one or more of the anti-UV additives described above.
  • Thermoplastic EVA compounded compositions in accordance with one or more embodiments of the present disclosure may incorporate a plasticizer to improve the processability and adjust the hardness of the composition.
  • Plasticizers in accordance with the present disclosure may include one or more of bis(2- ethylhexyl) phthalate (DEHP), di-isononyl phthalate (DINP), bis (n-butyl) phthalate (DNBP), butyl benzyl phthalate (BZP), di-isodecyl phthalate (DIDP), di-n-octyl phthalate (DOP or DNOP), di-o-octyl phthalate (DIOP), diethyl phthalate (DEP), di isobutyl phthalate (DIBP), di-n-hexyl phthalate, tri-methyl trimellitate (TMTM), tri- (2-ethylhexyl) trimellitate (TEHTM-MG), tri-
  • Thermoplastic EVA compounded compositions in accordance with one or more embodiments of the present disclosure may contain a plasticizer at a percent by weight (wt%) of the composition that ranges from a lower limit of 0.1 wt%, 0.5 wt% or 2 wt%, to an upper limit of 5 wt%, 7wt% or 10 wt%, where any lower limit may be paired with any upper limit.
  • wt% percent by weight
  • Thermoplastic EVA compounded 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.
  • polymer compositions in accordance with the present disclosure may be combined using any post-reactor melt mixture process, including kneaders, Banbury mixers, mixing rollers, extrusion processes with a single, double, or multi-screw extruder.
  • each component may be purified to specified standards and then combined to generate the final composition while minimizing the presence of reactants and degradation products.
  • a subset of the components may be combined by melt mixing followed by subsequent mixing steps, or all components may be melt mixed simultaneously.
  • the components to prepare the elastomeric EVA composition may be mixed with the polypropylene and the additives in a single mixture step.
  • the elastomeric EVA composition may be prepared in a prior step and subsequently may be mixed with the polypropylene and the additives to form the thermoplastic EVA compounded composition of the present disclosure.
  • raw materials may be added to a melt mixture device such as kneaders, banburys, or extruders in the form of powder, granules, flakes or dispersion in liquids as solutions, emulsions and suspensions of one or more components.
  • a melt mixture device such as kneaders, banburys, or extruders in the form of powder, granules, flakes or dispersion in liquids as solutions, emulsions and suspensions of one or more components.
  • the polymer composition is combined with a secondary polymer composition in a melt blend process. In one or more other embodiments, the polymer composition is combined with a secondary polymer composition in a dry blend process.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may have a hardness as determined in accordance with ASTM D2240 in a range having a lower limit selected from any of 70 Shore A, 80 Shore A and 85 Shore A, to an upper limit selected from any of 90 Shore A, 95 Shore A and 100 Shore A, where any lower limit may be paired with any upper limit.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may have a hardness as determined in accordance with ASTM D2240 in a range having a lower limit selected from any of 25 Shore D, 29 Shore D and 35 Shore D to an upper limit selected from any of 40 Shore D, 46 Shore D, and 54 Shore D, where any lower limit may be paired with any upper limit.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may have a melt flow index (MFI) at 190 °C and 2.16 kg as determined according to ASTM D 1238 in a range having a lower limit selected from any one of 2, 3, 4, and 5 g/lOmin, to an upper limit selected from any one of 9, 10, 11, and 12 g/lOmin, where any lower limit may be combined with any upper limit.
  • MFI melt flow index
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may have a melt flow index (MFI) at 190 °C and 5 kg as determined according to ASTM D 1238 in a range having a lower limit selected from any one of 20, 22, and 30 g/10 min to an upper limit selected from any one of 28, 35, 40, 48 g/lOmin and 60 g/10 min where any lower limit may be combined with any upper limit.
  • MFI melt flow index
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may have a density as determined according to ASTM D792 in a range having a lower limit selected from any one of 0.95, 0.98, or 0.99 g/cm 3 , to an upper limit selected from any one of 1.1, 1.2, and 1.25 g/cm 3 , where any lower limit may be combined with any upper limit.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may have a Tensile Modulus at 100% elongation as determined according to ASTM D638 in a range having a lower limit selected from any one of 5, 8 or 10 MPa, to an upper limit selected from any one of 15, 18 or 20 MPa, where any lower limit may be combined with any upper limit.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may have a Tensile Modulus at 300% elongation determined according to ASTM D638 in a range having a lower limit selected from any one of 3, 5.5 or 7 MPa, to an upper limit selected from any one of 9, 10 or 12 MPa, where any lower limit may be combined with any upper limit.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may have a Tensile Strength at Break as determined according to ASTM D638 in a range having a lower limit selected from any one of 5, 7 or 9 MPa, to an upper limit selected from any one of 10, 15 or 21 MPa, where any lower limit may be combined with any upper limit.
  • Thermoplastic EVA compounded compositions in accordance with the present disclosure may have a Tensile Elongation at Break (1% Secant) as determined according to ASTM D638 in a range having a lower limit selected from any one of 300%, 500% or 600%, to an upper limit selected from any one of 800%, 1000% or 1400%, where any lower limit may be combined with any upper.
  • articles in accordance with the present disclosure are formed by processing of the thermoplastic EVA compounded composition as disclosed herein in in any conventional plastic molding process such as injection molding, compression molding, rotomolding, thermoforming, extrusion molding and the like.
  • the article is an injection molded article, a thermoformed article, a foam, a compressed article, a coextruded article, a laminated article, a rotomolded article, an extruded article, monolayer articles, multilayer articles, and the like.
  • a multilayer article it is envisioned that at least one of the layers comprises the polymer composition of the present disclosure.
  • thermoplastic EVA compounded composition may be used in the manufacturing of articles, particularly including automotive parts such as aerodynamic deflectors, air dams, door panels, instrument panels, trim parts, bumpers, steering systems, hoses, gaskets, and foams.
  • automotive parts such as aerodynamic deflectors, air dams, door panels, instrument panels, trim parts, bumpers, steering systems, hoses, gaskets, and foams.
  • articles that may be produced using polymer compositions in accordance with the present disclosure include injected articles and parts, foams, expanded articles, thermoformed articles, domestic utilities, technical parts, air ducts, cushion garnish and back frames, masterbatches, and the like.
  • polymer formulations are prepared in accordance with the present disclosure from a mixture of an elastomeric EVA composition VA4018R and polypropylene homopolymer PP H301, both commercially available resins by Braskem. Formulations are shown below in Table 1, while assayed physical properties are shown below in Table 2.

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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)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Les compositions de polymère mélangées et leurs procédés de fabrication comprennent une composition d'EVA élastomère dans une quantité allant d'environ 46 à 70% en poids de la composition de polymère; et un polypropylène en une quantité allant d'environ 20 à 40% en poids de la composition de polymère. Les procédés comprennent le mélange d'une composition d'EVA élastomère avec du polypropylène, et l'extrusion du mélange de composition d'EVA élastomère et de polypropylène.
EP19823990.7A 2018-11-13 2019-11-13 Compositions contenant de l'eva présentant des propriétés mécaniques améliorées et articles et procédés associés Pending EP3880752A1 (fr)

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US201862760210P 2018-11-13 2018-11-13
PCT/IB2019/026292 WO2020099939A1 (fr) 2018-11-13 2019-11-13 Compositions contenant de l'eva présentant des propriétés mécaniques améliorées et articles et procédés associés

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EP (1) EP3880752A1 (fr)
JP (1) JP2022507313A (fr)
KR (1) KR20210099589A (fr)
AR (1) AR117076A1 (fr)
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WO (1) WO2020099939A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2022074465A1 (fr) * 2020-10-07 2022-04-14 Braskem S.A. Compositions à base d'eva pour articles chaussants
CN113930169B (zh) * 2021-11-01 2023-05-12 南京工程学院 一种耐热型eva胶膜及其制备方法

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JPS61252257A (ja) * 1985-04-30 1986-11-10 Toyoda Gosei Co Ltd オレフイン系熱可塑性エラストマ−
EP0472512B1 (fr) * 1990-08-21 1996-03-06 Advanced Elastomer Systems, L.P. Polymères d'oléfines thermoplastiques réticulés dynamiquement et son procédé de préparation
WO2009146438A1 (fr) * 2008-05-30 2009-12-03 Dow Global Technologies Inc. Composés polyoléfiniques compatibles à deux ou trois composants
BR112012005424A2 (pt) 2009-09-09 2017-06-13 Braskem Sa método para produzir n-propanol, e, microorganismo
BR102012025160B1 (pt) 2012-10-02 2017-05-23 Braskem Sa composição elastomérica não expandida à base de polímero de etileno e acetato de vinila e uso da mesma para confecção de calçados

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JP2022507313A (ja) 2022-01-18
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BR112021009216A2 (pt) 2021-08-03
KR20210099589A (ko) 2021-08-12

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