WO2017064508A1 - Polymer blends - Google Patents

Polymer blends Download PDF

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Publication number
WO2017064508A1
WO2017064508A1 PCT/GB2016/053195 GB2016053195W WO2017064508A1 WO 2017064508 A1 WO2017064508 A1 WO 2017064508A1 GB 2016053195 W GB2016053195 W GB 2016053195W WO 2017064508 A1 WO2017064508 A1 WO 2017064508A1
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WIPO (PCT)
Prior art keywords
compatibilizer
polymer blend
particulate
polymer
weight
Prior art date
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Ceased
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PCT/GB2016/053195
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English (en)
French (fr)
Inventor
Fatima REBIH
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.)
Imerys Minerals Ltd
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Imerys Minerals Ltd
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Application filed by Imerys Minerals Ltd filed Critical Imerys Minerals Ltd
Priority to JP2018502266A priority Critical patent/JP6890576B2/ja
Priority to KR1020187003668A priority patent/KR20180070544A/ko
Priority to EP16784263.2A priority patent/EP3362510A1/en
Priority to US15/735,633 priority patent/US11059962B2/en
Priority to CN201680039702.8A priority patent/CN107835836A/zh
Priority to AU2016339049A priority patent/AU2016339049B2/en
Priority to BR112017026566-4A priority patent/BR112017026566B1/pt
Publication of WO2017064508A1 publication Critical patent/WO2017064508A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02Organic and inorganic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/14Peroxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • 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
    • C08L23/06Polyethene
    • 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
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08Treatment with low-molecular-weight non-polymer organic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/005Additives being defined by their particle size in general
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/08Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • 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
    • C08L2207/20Recycled plastic

Definitions

  • the present invention is directed to a compatibilizer for a polymer blend, the compatibilizer comprising a particulate and an organic linker on a surface of the particulate, wherein the organic linker is a basic form of an organic acid comprising an oxygen-containing acid functionality and at least one carbon-carbon double bond.
  • the present invention is directed to the use of an organic linker as defined in the first or second aspects in a compatibilizer for a polymer blend.
  • the present invention is directed to a polymer blend comprising a compatibilizer according to the first or second aspects.
  • the present invention is directed to a method for making a compatibilizer for a polymer blend, the method comprising combining an organic linker as defined the first or second aspects with a particulate.
  • the present invention is directed to a method for making a polymer blend comprising a compatibilizer, the method comprising preparing, providing or obtaining a compatibilizer according to the first or second aspects, and compounding the compatibilizer with a polymer blend.
  • the present invention is directed to the use of a polymer blend according to the fifth aspect in the manufacture of an article.
  • the present invention is directed to a method for making an article according the eighth aspect, comprising forming the article from a polymer blend according to the fifth aspect, optionally wherein forming comprises extrusion or moulding, for example, injection or blow moulding.
  • the compatibilizer is for use in a polymer blend, i.e., a polymer composition which comprises a mixture of different polymer types.
  • the compatibilizer comprises a particulate and an organic linker on a surface of the particulate.
  • the organic linker has an oxygen-containing acid functionality.
  • the organic linker is a basic form of an organic acid.
  • basic form is meant that the organic acid is at least partially deprotonated, e.g., by dehydrating an organic acid to form the corresponding oxyanion.
  • the basic form of an organic acid is the conjugate base of the organic acid.
  • the organic acid (and, thus, the organic linker) comprises at least one carbon-carbon double bond.
  • the non-polymeric species has a molecular mass of no greater than about 800 g/mol, or no greater than about 600 g/mol, or no greater than about 500 g/mol, or no greater than about 400 g/mol, or no greater than about 300 g/ mol, or no greater than about 200 g/mol.
  • the non-polymeric species comprises no more than about 50 carbon atoms, or no more than about 40 carbon atoms, or no more than about 30 carbon atoms, or no more than about 25 carbon atoms, or no more than about 20 carbon atoms, or no more than about 15 carbon atoms.
  • the organic linker is the conjugate base of an organic acid, for example, a carboxylate or phosphate or phosphite or phosphinate or amino acid.
  • the organic linker is a carboxylate.
  • the organic linker includes a maleimide ring (e.g., with an amide carboxylate functionality coordinates/associates with the surface of the particulate and an a carbon- carbon double bond coordinates/associates with the different polymer species in the polymer blend).
  • the organic linker comprises at least one carbon atom in addition to the carbon-carbon double bond. In certain embodiments, the organic linker comprises at least two carbon atoms, or at least three carbon atoms, or at least four carbon atoms, or at least five carbon atoms in addition to the carbon-carbon double bond. In certain embodiments, the organic linker comprises at least six carbon atoms, for example, a chain of at least six carbon atoms, including the at least one carbon- carbon double bond. In certain embodiments, the organic linker comprises only one carbon-carbon double bond. In certain embodiments, the organic linker comprises two carbon-carbon double bonds. In certain embodiments, the organic linker comprises three carbon-carbon double bonds.
  • a is from 6 to 20, for example, from 6 to 18, or 6 to 16, or 6 to 14, or 6 to 12, or 6 to 10, or 7 to 9. In certain embodiments, a is 8.
  • the unsaturated fatty acid may be selected from one of myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucuc acid and docosahexanoic acid.
  • the unsaturated fatty acid may be oleic acid, i.e., in certain embodiments, the compatibilizer comprises particulate (for example, mineral particulate) and the basic form of oleic acid.
  • the compatibilizer consists of particulate (for example, mineral particulate) and the basic form of oleic acid.
  • the organic acid is derived from an unsaturated fatty acid.
  • the organic acid is undecylenic acid, i.e., the organic linker is the basic form of undecylenic acid.
  • the compatibilizer consists of particulate (for example, mineral particulate) and the basic form of undecylenic acid.
  • the particulate is an inorganic particulate, for example, a mineral.
  • the dgo (also referred to as the top cut) of the inorganic particulate may be less than about 150 ⁇ , for example, less than about 125 ⁇ for example, less than about 100 ⁇ for example, less than about 75 ⁇ , for example, less than about 50 ⁇ , for example, less than about 25 ⁇ , for example, less than about 20 ⁇ , for example, less than about 15 ⁇ , for example, less than about 10 ⁇ , for example, less than about 8 ⁇ , for example, less than about 6 ⁇ , for example, less than about 4 ⁇ , for example, less than about 3 ⁇ or, for example, less than about 2 ⁇ .
  • the dgo may be less than about 25 ⁇ .
  • the particulate has a dgo of from about 1.0 to about 10 ⁇ , for example, from about 1.0 to about 8 ⁇ , or from about 1.5 ⁇ to about 6 ⁇ , or from about 1.5 ⁇ to about 5 ⁇ , or from about 1.5 ⁇ to about 4 ⁇ , or from about 1.5 ⁇ to about 3 ⁇ , or from about 1.5 ⁇ to about 2.5 ⁇ , or from about 1.75 ⁇ to about 2.25 ⁇ , or from about 1.9 ⁇ to about 2.1 ⁇ .
  • the compatibilizer is present in the polymer blend in an amount ranging from about 5 % by weight to about 35 % by weight, for example, from about 10 % by weight to about 30 % by weight, or from about 10 % by weight to about 25 % by weight, or from about 12 % by weight to about 25 % by weight, or from about 15 % by weight to about 25 % by weight, or from about 10 % by weight to about 20 % by weight, or from about 20 % by weight to about 30 % by weight, based on the total weight of the polymer blend.
  • the organic linker is present in the compatibilizer in an amount greater than about 0.05 wt. %. In further embodiments, the organic linnker is present in the compatibilizer in an amount ranging from about 0.1 to 2 wt.
  • the sufficient amount will vary depending on, for example, the particle size distribution of the particulate and the specific form of organic linker. In certain embodiment, a sufficient amount ranges from about 0.1 to about 5 wt. %, based on the total weight of the compatibilizer, for example, from about 0.5 to about 2 wt. %.
  • the organic linker may be added to the particulate in a step in which the particulate is mechanically de-aggregated.
  • the organic linker may be combined during de-aggregation carried out in a milling machine.
  • the method comprises mixing an organic acid precursor of the organic linker with the particulate while the particulate is maintained in a dispersed state, and heating the mixture, for example, at a temperature of no greater than about 80 °C, or any of the other temperature or ranges described above. Heating facilitates (i.e., by dehydration) the conversion of at least a portion of the organic acid to the basic form of the organic acid.
  • substantially all of the organic acid is converted to its basic form.
  • the compatibilizer may be prepared in the presence of a peroxide-containing additive, as described below.
  • HDPE may constitute from about 50 % to about 95 % by weight of the polymer blend (based on the total weight of the polymer of the filled polymer resin), for example, from about 60 % to about 90 % by weight, or from about 70 % to about 90 % by weight, of from about 70 % to about 85 % by weight, or from about 70 % to about 80 % by weight, or from about 75 % to about 80 % by weight of the polymer blend (based on the total weight of the polymer of the polymer blend).
  • the HDPE is mixture of HDPE from different sources, for example, from different types of post-consumer polymer waste, e.g., recycled blow- moulded HDPE and/or recycled injection moulded HDPE.
  • the polymer blend comprises up to about 20 % by weight of polymers other than HDPE such as, for example, LDPE, LLDPE and polypropylene, any or all of which may be recycled from polymer waste, e.g., post-consumer polymer waste.
  • the recycled polymer comprises up to about 20 % by weight polypropylene, based on the total weight of the recycled polymer, for example, from about 1 % to about 20 % by weight, or from about 5 % to about 18 % by weight, or from about 10 % to about 15 % by weight, or from about 12 to about 14 % by weight polypropylene.
  • the polymer blend comprises no more than about 20 % by weight of virgin polymer (based on the total weight of polymer in the polymer blend), for example, no more than about 15 % by weight of virgin polymer, or no more than about 10 % by weight of virgin polymer, or no more than 5 % by weight of virgin polymer, or no more than about 2 % by weight of virgin polymer, or no more than about 1 % by weight of virgin polymer, or no more than about 0.5 % by weight of virgin polymer, or no more than about 0.1 % by weight of virgin polymer.
  • the polymer blend is free of virgin polymer.
  • the polymer blend may additionally comprise a peroxide-containing additive.
  • the peroxide-containing additive comprises di-cumyl peroxide or 1 , 1- Di(tert-butylperoxy)-3,3,5-trimethylcyclohexane.
  • the peroxide-containing additive may not necessarily be included with the compatibilizer and instead may be added during the compounding of the compatibilizer and the mixture of different polymer types, as described herein.
  • the inclusion of a peroxide-containing additive may promote cross-linking of the polymer chains.
  • the inclusion of a peroxide- containing additive may promote polymer chain scission.
  • the peroxide-containing additive may be present in amount effective to achieve the desired result. This will vary between compatibilizer and may depend upon the precise composition of the compatibilizer and the polymer.
  • the peroxide-containing additive may be present in an amount equal to or less than about 1 wt. % based on the weight of the polymer blend to which the peroxide-containing additive is to be added, for example, equal to or less than about 0.5 wt. %, for example equal to or less than about 0.3 wt. %, for example, equal to or less than about 0.1 wt %, for example equal to or less than about 0.09 wt. %, or for example equal to or less than about 0.08 wt. % or for example, equal to or less than about 0.06 wt. %.
  • the peroxide-containing additive if present, is present in an amount greater than about 0.01 wt. % based on the weight of the polymer blend.
  • the polymer blend may additionally comprise an antioxidant.
  • Suitable antioxidants include, but are not limited to, organic molecules consisting of hindered phenol and amine derivatives, organic molecules consisting of phosphates and lower molecular weight hindered phenols, and thioesters.
  • Exemplary antioxidants include Irganox 1010 and Irganox 215, and blends of Irganox 1010 and Irganox 215.
  • the polymer blend comprises an impact modifier, for example, up to about 20 % by weight of an impact modifier, based on the total weight of the filled polymer resin, for example, from about 0.1 % by weight to about 20 % by weight, or from about 0.5 % by weight to about 15 % by weight, or from about 1 % by weight to about 12.5 % by weight, or from about 2 % by weight to about 12.
  • an impact modifier for example, up to about 20 % by weight of an impact modifier, based on the total weight of the filled polymer resin, for example, from about 0.1 % by weight to about 20 % by weight, or from about 0.5 % by weight to about 15 % by weight, or from about 1 % by weight to about 12.5 % by weight, or from about 2 % by weight to about 12.
  • the impact modifier is an elastomer, for example, a polyolefin elastomer.
  • the polyolefin elastomer is a copolymer of ethylene and another olefin (e.g., an alpha-olefin), for example, octane, and/or or butene and/or styrene.
  • the impact modifier is a copolymer of ethylene and octene.
  • the impact modifier is a copolymer of ethylene and butene.
  • the impact modifier is a recycled (e.g., post industrial) impact modifier.
  • the impact modifier for example, polyolefin copolymer as described above, such as an ethylene-octene copolymer, has a density of from about 0.80 to about 0.95 g/cm 3 and/or a MFI of from about 0.2 g/10 min (2.16 kg@190 °C) to about 30 g/10 min (2.16 kg@190 °C), for example, from about 0.5 g/10 min (2.16 kg@190 °C) to about 20 g/10 min (2.16 kg@190 °C), or from about 0.5 g/10 min (2.16 kg@190 °C) to about 15 g/10 min (2.16 kg@190 °C), or from about 0.5 g/10 min (2.16 kg@190 °C) to about 10 g/10 min (2.16 kg@190 °C), or from about 0.5 g/10 min (2.16 kg@190 °C) to about 7.5 g/10 min (2.16 kg@190 °C), or from about 0.5 g/10 min (2.
  • the impact modifier is an ethylene-octene copolymer having a density of from about 0.85 to about 0.86 g/cm 3 .
  • exemplary impact modifiers are polyolefin elastomers made by DOW under the Engage(RTM) brand, for example, Engage (RTM) 8842.
  • the compounded polymer blend may additionally comprise an antioxidant, as described herein.
  • the impact modifier is a copolymer based on styrene and butadiene, for example, a linear block copolymer based on styrene and butadiene.
  • the impact modifier may have a MFI of from about from about 1 to about 5 g/10min (200°C @ 5.0kg), for example, from about 2 g/10min (200°C @ 5.0kg) to about 4 g/10min (200°C @ 5.0kg), or from about 3 g/10min (200°C @ 5.0kg) to about 4 g/10min (200°C @ 5.0kg).
  • the linear block copolymer may be a recycled linear block copolymer.
  • the impact modifier is a copolymer based on styrene and isoprene, for example, a linear block copolymer based on styrene and isoprene.
  • the impact modifier may have a MFI of from about from about 5 to about 20 g/10min (230°C @ 2.16), for example, from about 8 g/10min (230°C @ 2.16kg) to about 15 g/10min (230°C @ 2.16kg), or from about 10 g/10min (230°C @ 2.16kg) to about 15 g/10min (230°C @ 2.16kg).
  • the linear block copolymer may be recycled.
  • the impact modifier there is crosslinking between the impact modifier and one or more polymers of the polymer blend, for example, in embodiments in which the impact modifier is a linear block copolymer based on styrene and butadiene, or on styrene and isoprene, and/or the polymer blend comprises PE.
  • the impact modifier may be miscible in the polymer blend.
  • the compatibilizer is prepared in a first location and is transported to a second location and combined with the mixture of different polymer types.
  • the polymer blend and compatibilizer are compounded in the presence of a peroxide-containing additive, as described herein.
  • the polymer blend comprises a secondary filler component, for example, talc, which may added during compounding of the polymer blend and compatibilizer and optional peroxide-containing additive.
  • talc a secondary filler component
  • Compounding per se is a technique which is well known to persons skilled in the art of polymer processing and manufacture. It is understood in the art that compounding is distinct from blending or mixing processes conducted at temperatures below that at which the constituents become molten.
  • Compounding may be carried out using a twin screw compounder, for example, a Baker Perkins 25 mm twin screw compounder.
  • the polymers, compatibilizer and optional peroxide containing additive may be premixed and fed from a single hopper. Alternatively, at leas the polymers and compatibilizer may be fed from separate hoppers.
  • the resulting melt may be cooled, for example, in a water bath, and then pelletized. Test pieces may be injection moulded, or extruded, or cast or blown.
  • Polymer articles may then be extruded, compression moulded or injected moulded using conventional techniques known in the art, as will be readily apparent to one of ordinary skill in the art.
  • the article of manufacture is the form of one of the following: panels (e.g., automotive panels), pallets, pipes, doors, shutters, awnings, shades, signs, frames, window casings, mobile phone casings, pails, backboards, wallboards, flooring, tiles, railroad ties, forms, trays, tool handles, stalls, bedding, dispensers, staves, totes, barrels, boxes, packing materials, baskets, racks, casings, binders, dividers, walls, mats, frames, bookcases, sculptures, chairs, tables, desks, art, toys, games, wharves, piers, boats, masts, septic tanks, substrates, computer housings, above- and below-ground electrical casings, PCB covers, furniture, picnic tables, tents, playgrounds, benches, shelters, sporting goods, bedpans, plaques, trays, hangers, servers, pools, insulation, caskets, bookcovers, canes, crutches, luggage buckle and clips,
  • panels
  • the polymer composition may be used to modify, for example, enhance or improve, a mechanical property of an article of manufacture, by forming the article of manufacture from the polymer blend.
  • the mechanical property may be selected from one or more of resilience (toughness), elongation at break, flexural modulus (stiffness) and deflection (ductility).
  • resilience toughness
  • elongation at break elongation at break
  • flexural modulus elongation at break
  • flexural modulus elongation at break
  • deflection ductility
  • the coupling effect means that less polymer (recycled or virgin) can be used (i.e., by replacing a portion with the compatibilizer) without adversely effecting mechanical properties and, in some embodiments, improving mechanical properties (with the concomitant cost benefits).
  • the resilience of the article from a polymer blend filled with the compatibilizer is at least about 50 % greater than an article formed from a polymer blend filled with only the particulate of the compatibilizer, for example, at least about 75 % greater, or at least about 100 % greater (i.e., double the resilience), or at least about 125 % greater, or at least about 150 % greater, or at least about 175 % greater, or at least about 200% greater.
  • the resilience of the article formed from a polymer blend filled with the compatibilizer is no more than about 300 % greater than an article formed from a polymer blend filled with only the particulate of the compatibilizer, for example, no more than about 275 % greater, or no more than about 250 % greater.
  • the flexural modulus of an article formed from the polymer blend filled with the compatibilizer is from about 92 % to about 95 % of the flexural modulus of an article formed from a polymer blend filled with only the particulate of the compatibilizer.
  • the article of manufacture has:
  • Flexural modulus may be determined in accordance with ISO 178. Additional components
  • the polymer blend comprises a coupling modifier in addition to the compatabilizer.
  • the coupling modifier comprises a compound including a terminating propanoic group or ethylenic group with one or two adjacent carbonyl groups.
  • a function of the coupling modifier is to couple polymeric species present in the polymer blend. Without wishing to be bound by theory, it is believed that coupling involves a physical (e.g., steric) and/or chemical (e.g., chemical bonding, such as covalent or van der Waals) interaction between the polymers and the coupling modifier.
  • the coupling modifier has a formula (1):
  • X is O and m is 1 to 4 or X is N and m is 1 ;
  • Y is Ci-18-alkylene or C2-i8-alkenylene
  • B is C2-6-alkylene; n is 0 to 5;
  • A-X- is the residue of acrylic acid, optionally wherein (0-B-CO) n is the residue of ⁇ -valerolactone or ⁇ -caprolactone or a mixture thereof, and optionally wherein n is zero.
  • A-X- is the residue of maleimide, optionally wherein (0-B-CO) n is the residue of ⁇ -valerolactone or ⁇ -caprolactone or a mixture thereof, and optionally wherein n is zero.
  • coupling modifiers are ⁇ -carboxy ethylacrylate, ⁇ - carboxyhexylmaleimide, 10-carboxydecylmaleimide and 5-carboxy pentyl maleimide.
  • Exemplary coupling modifiers and there methods of preparation are described in US-A- 7732514, the entire contents of which is hereby incorporated by reference.
  • the coupling modifier is ⁇ -acryloyloxypropanoic acid or an oligomeric acrylic acid of the formula (2):
  • n is 1 , or 2, or 3, or 4, or 5, or 6.
  • the oligomeric acrylic acid of formula (2) may be prepared by heating acrylic acid in the presence of 0.001 to 1 % by weight of a polymerization inhibitor, optionally under elevated pressure and in the presence of an inert solvent, to a temperature in the range from about 50°C to 200°C.
  • a polymerization inhibitor optionally under elevated pressure and in the presence of an inert solvent
  • the coupling modifier may be present in an amount effective to achieve the desired result.
  • the coupling modifier may be present in an amount equal to or less than about 5 wt. % based on the total weight of the particulate of the polymer blend, for example equal to or less than about 2 wt. % or, for example equal to or less than about 1.5 wt. % or, for example, equal to or less than about 1.0 wt. % or, for example, equal to or less than about 0.75 wt. %, or equal to or less than about 0.5 wt. %.
  • the coupling modifier is present in an amount equal to or greater than about 0.1 wt. %.
  • Compatibilizer for a polymer blend comprising a particulate and an organic linker on a surface of the particulate, wherein the organic linker is a basic form of an organic acid comprising an oxygen-containing acid
  • Compatibilizer for a polymer blend comprising a particulate and organic linker on a surface of the particulate, wherein the compatibilizer is obtained by at least partially dehydrating an organic acid having an oxygen- containing acid functionality and comprising at least one carbon-carbon double bond in the presence of the particulate.
  • the organic linker is the conjugate base of said organic acid.
  • the organic acid is an unsaturated fatty acid or derived from an unsaturated fatty acid.
  • b is equal to or greater than 1
  • c is equal to or greater than 0, provided that b + c is at least 2;
  • Z is a carboxylate group, a phosphate group, a phosphite or a phosphinate group. 7.
  • the particulate is an inorganic particulate, for example, a mineral particulate.
  • the particulate is an alkaline earth metal carbonate or sulphate, such as calcium carbonate, magnesium carbonate, dolomite, gypsum, a hydrous kandite clay such as kaolin, halloysite or ball clay, an anhydrous (calcined) kandite clay such as metakaolin or fully calcined kaolin, talc, mica, perlite or diatomaceous earth, or magnesium hydroxide, or aluminium trihydrate, or combinations thereof.
  • alkaline earth metal carbonate or sulphate such as calcium carbonate, magnesium carbonate, dolomite, gypsum, a hydrous kandite clay such as kaolin, halloysite or ball clay, an anhydrous (calcined) kandite clay such as metakaolin or fully calcined kaolin, talc, mica, perlite or diatomaceous earth, or magnesium hydroxide, or aluminiu
  • Method for making a polymer blend comprising a compatibilizer comprising preparing, providing or obtaining a compatibilizer according to any one of numbered paragraphs 1-18, and compounding the compatibilizer with a polymer blend, optionally wherein the compatibilizer is prepared in accordance with the method of numbered paragraph 26.
  • paragraphs 22-24 or obtainable by the method of any one of numbered paragraphs 27-29.
  • resilience which is at least about 50 % greater than an article formed from a polymer blend filled with only the particulate of the compatibilizer; and/or (ii) a flexural modulus which is at least about 92 % of the flexural modulus of an article formed from a polymer blend filled with only the particulate of the compatibilizer.
  • a method for making an article according to numbered paragraph 30, comprising forming the article from a polymer blend according to any one of numbered paragraphs 22-24, optionally wherein forming comprises extrusion or moulding, for example, injection or blow moulding.
  • the polymer blend comprises a mixture of polyethylene (PE) and polypropylene PP, for example, a mixture of high density PE (HDPE) and PP.
  • PE polyethylene
  • HDPE high density PE
  • polymer blend comprises at least about 50 % by weight recycled polymer, based on the total weight of polymer in the polymer blend.
  • polymer blend comprises up to about 70 % by weight of compatibilizer, based on the total weight of the polymer blend, for example, from about 10 % by weight to about 30 % by weight of compatibilizer.
  • the particulate was a ground calcium carbonate having a dso of 1 ⁇ and a dgo of 2 ⁇ .
  • the compatibilizer was prepared by the following two-step process: First Step: The unsaturated carboxylic acid was added to the particulate while it was maintained in a dispersed state using a Steele and Cowlishaw high shear mixer running at 3000 rpm and heated to 30°C.
  • PE/PP (75/25 wt. %/wt. %) blends were compounded with a twin screw- extruder in presence of various amounts (15 wt. % and 20 wt. %) of compatibilizer and in the presence of dicumyl peroxide.
  • Comparative polymer blends comprising particulate only (i.e., without compatabilizer) were also prepared.
  • Example 2 mechanical testing of parts made from polymer blend of Example 1

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  • Medicinal Chemistry (AREA)
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PCT/GB2016/053195 2015-10-14 2016-10-14 Polymer blends Ceased WO2017064508A1 (en)

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