Polymer material

Abstract

A method of treating a mass of a polymeric material to reduce odor thereof, which may comprise recycled polystyrene or recycled polyolefin, the method comprising: (i) selecting a first material comprising a polymeric material; and (ii) contacting the first material with a zeolite Y; wherein the zeolite Y has a Si: Al molar ratio in the range of from 5.0: 1 to 100: 1. Mixtures in the form of products comprising a polymeric material and zeolite Y, such as molded articles, pellets, pellets, are described as formulations used in the process.

Description

[0001] The present invention relates to polymeric materials, in particular, but not exclusively, to formulations for addition to polymeric materials comprising recyclates to reduce the content of odour causing species that can be released from the recyclates and to facilitate the use of higher contents of recyclates in the products.

[0002] Regulations and brand owner targets require increasing the content of recyclates used in polymeric materials. However, recyclates, such as polyolefin (PO) post consumer resin (PCR), are contaminated with a variety of malodour causing species. The odour originates from a variety of materials that the polymers come into contact with during their life cycle, extraneous contaminants and the decomposition of these substances under the action of heat, light, microorganisms and other degradation pathways, as well as degradation of the polymers during processing. As a result, mechanically recycled PO (rPO) has an unpleasant odour that limits its use in markets with sensory requirements.

[0003] Due to the contamination with malodour causing species, the recycling of other polymeric materials [such as acrylonitrile butadiene styrene (ABS), polyvinyl butyral (PVB), polyvinyl chloride (PVC), acrylonitrile styrene acrylate (ASA), polymethyl methacrylate (PMMA), polystyrene (PS) or polyolefin (PO)] can also become more difficult.

[0004] The above problems can be addressed in a way that aims to reduce the unpleasant odour associated with recycled polymeric materials, such as rPO:

[0005] (i) Incorporation of adsorbents into rPO. However, in this approach the adsorption is inversely proportional to the temperature and the masterbatch tends to affect the density and other polymer properties. As a result, this approach is inefficient and has limited effect.

[0006] (ii) Incorporation of reactive masterbatches into rPO (such as zinc ricinoleate provided by ColorMatrix or Triple A™). However, in this approach there is high chemical selectivity to individual species, which means that there can be no effect on most of the odour active species in the rPO. Furthermore, new odour species can be generated, requiring a high let-down ratio.

[0007] (iii) thermal physical processing, such as vacuum degassing or hot air / nitrogen stripping of rPO. However, disadvantageously, these processes require significant upstream investment and are costly. Furthermore, removal of less volatile species is also challenging. (iv) Chemical recycling of rPO, such as using chemical solvents or processes. This is an early stage technology requiring significant capital investment.

[0008] (v) Use of materials loaded with aqueous species which can be incorporated during the extrusion process to accelerate removal of odour species through the vacuum port.

[0009] It is an object of preferred embodiments of the present application to address the above problems.

[0010] It is an object of preferred embodiments of the present application to provide a process which can use increased levels of recyclate.

[0011] It is an object of preferred embodiments of the present application to provide a means of reducing odour associated with recyclate.

[0012] According to a first aspect of the present application, there is provided a process for treating a quantity of polymeric material, the process comprising:

[0013] (i) selecting a first material comprising polymeric material; and

[0014] (ii) contacting the first material with a zeolite Y.

[0015] The zeolite Y is suitably a zeolite Y as defined by the International Zeolite Association (IZA). Thus, it suitably has a FAU framework.

[0016] The Si:Al molar ratio of the zeolite Y is suitably at least 3.0, preferably at least 4.0, more preferably at least 5.0. The molar ratio can be at least 5.1 : 1 or at least 5.2: 1. The molar ratio can be in the range 5.0: 1 to 100: 1, preferably in the range 5.1 : 1 to 100: 1, more preferably in the range 5.1 : 1 to 90: 1 or in the range 5.2: 1 to 85: 1. In some cases, the molar ratio can be in the range 5.0: 1 to 10: 1.

[0017] The zeolite Y can have a counterion selected from H + , Na + and NH4 + . The counterion is preferably selected from H + and NH4 + .

[0018] The zeolite Y can have a surface area of at least 410 m 2 / g, suitably at least 450 m2 / g, preferably at least 500 m 2 / g, more preferably at least 600 m 2 / g, especially at least 650 m 2 / g. In all cases, the surface area can be at least 700 m 2 / g. The surface area can be less than 950 m 2 / g or less than 800 m 2 / g. The surface area can range from 410 to 950 m 2 / g. The surface area described herein can be determined by N2adsorption using the Brunauer-Emmett-Teller (BET) surface area analysis.

[0019] Preferably, the zeolite has strong Bronstead activity, which can be assessed by measuring the aqueous slurry of the candidate zeolite itself using a pH meter.

[0020] Preferably, the method is a method of treating a bulk polymer material to reduce its odour. The method can comprise treating the first material to produce a bulk polymer material having less odour than the odour associated with the first material of polymer material selected in step (i). For example, the method can be used to treat the bulk polymer material to reduce the concentration of a substance having a high odour activity value. In some cases, the method can be used to reduce the concentration of a substance to less than its organoleptic threshold.

[0021] The method can comprise treating the first material to produce a bulk polymer material having a reduced volatile emissions. For example, the total terpinenes content (as suitably assessed according to Assessment #1) of the first material can be reduced following treatment of the first material. Typically, the content of other highly odour active substances can be reduced as described in the examples.

[0022] Preferably, the method comprises treating a first material comprising a recycled polymer material. The method enables a higher content of recycled polymer material to be used in the production of an article than would otherwise be possible. The method can comprise, in step (i), selecting a first material of polymer material.

[0023] The recycled polymer material can be acrylonitrile butadiene styrene (ABS), polyvinyl butyral (PVB), polyvinyl chloride (PVC), acrylonitrile styrene acrylate (ASA), polymethyl methacrylate (PMMA), polystyrene (PS) or polyolefin (PO).

[0024] In embodiment A1, the polymer material in the first material can comprise at least 90 wt%, at least 95 wt% or at least 99 wt% recycled polymer material.

[0025] The recycled polymer material can be recycled polystyrene or recycled polyolefin, such as polyethylene and / or polypropylene. In the embodiment A1, the first material can comprise at least 90 wt%, at least 95 wt% or at least 99 wt% of recycled polymer material. In this case, the recycled polymer material can comprise polystyrene or polyolefin (but preferably not a mixture of polystyrene and polyolefin). When the recycled polymer material comprises polyolefin, it can comprise at least 50 wt% of polyethylene and / or at least 50 wt% of polypropylene. In some embodiments, when the recycled polymer material comprises polyolefin, it can comprise at least 90 wt%, at least 95 wt% or at least 99 wt% of polyethylene, or at least 90 wt%, at least 95 wt% or at least 99 wt% of polypropylene. In some cases, the recycled polymer material can comprise a mixture of polyolefins.

[0026] In the embodiment A1, pellets doped with the zeolite can be produced, wherein the pellets can comprise a high content of recycled polymer material, wherein the odor of the recycled polymer material is suitably reduced. Such pellets can subsequently be used in a downstream process, for example mixed with virgin resin and from which molded articles are made.

[0027] In the embodiment A2, the first material can comprise a first polymer material and a recycled polymer material.

[0028] Unless otherwise specified herein, the recycled polymer material can comprise waste and scrap polymer material, post-consumer recyclate (PCR) and / or post-industrial recyclate (PIR). The recycled polymer material can comprise recycled polyolefin, such as recycled polyethylene and / or polypropylene. The recycled polymer material can comprise PCR.

[0029] In the process, preferably, the first material is not devolatilized after step (i). Preferably, the first material is not devolatilized before step (i). The term “devolatilization” can refer to a process of removing unwanted volatile contaminants (e.g. dissolved gases, solvents, unreacted monomers, etc.) from a polymer melt or solution. The devolatilization process is typically driven by superheating the volatile components of the polymer melt / solution in a screw extruder, followed by rapid depressurization of the melt / solution. Devolatilization is costly and time-consuming to perform; the need to avoid devolatilization can be commercially advantageous.

[0030] The first polymer material can comprise polystyrene or polyolefin, such as polyethylene and / or polypropylene. The first polymer material preferably does not comprise any recycled polymer material, such as any PCR. The first polymer material can comprise virgin polymer material, such as virgin polystyrene or virgin polyolefin. The first polymer material can be virgin polyethylene or virgin polypropylene. It preferably comprises virgin polyethylene.

[0031] The first polymeric material can comprise at least 80 wt%, at least 90 wt% or at least 95 wt% virgin polystyrene or virgin polyolefin. The first polymeric material can comprise at least 50 wt%, at least 75 wt% or at least 95 wt% virgin polyethylene; or the first polymeric material can comprise at least 50 wt%, at least 75 wt% or at least 95 wt% virgin polypropylene.

[0032] In embodiment A2, pellets can be prepared incorporating the zeolite, the first polymeric material and the recycled polymeric material. The pellets can then be used in downstream processes, for example optionally mixed with virgin resin and thereby made into moulded articles.

[0033] In the embodiment A2, the first material can comprise 20 to 80 wt% of the first polymeric material and 20 to 80 wt% of recycled polymeric material. The first material can comprise 50 to 80 wt% (for example 50 to 75 wt%, 50 to 70 wt% or 50 to 65 wt%) of the first polymeric material and 20 to 50 wt% (for example 25 to 50 wt%, 30 to 50 wt% or 35 to 50 wt%) of recycled polymeric material.

[0034] In embodiment A3, the polymeric material in the first material can comprise a significant amount of virgin polymeric material. For example, the polymeric material in the first material can comprise at least 90 wt%, at least 95 wt% or at least 99 wt% virgin polymeric material, for example virgin polyolefin. This can be advantageous for the production of products for use in automotive applications.

[0035] A preparation comprising the zeolite Y can be used in step (ii). The preparation can comprise at least 10 wt%, preferably at least 20 wt%, more preferably at least 30 wt%, especially preferably at least 40 wt% of the zeolite Y. The preparation can comprise less than 90 wt% or less than 80 wt% of the zeolite Y. The preparation preferably comprises 10 to 80 wt%, more preferably 20 to 60 wt% of the zeolite Y.

[0036] The sum of the wt% of all zeolites in the preparation can be at least 10 wt%, preferably at least 20 wt%, more preferably at least 30 wt%, especially at least 40 wt%. The preparation can comprise less than 90 wt% or less than 80 wt% of zeolites in total. Preferably, the preparation comprises 10 to 80 wt% of zeolites in total, more preferably 20 to 60 wt%.

[0037] The total weight % of zeolites having Y structure in the formulation can be at least 10 wt%, preferably at least 20 wt%, more preferably at least 30 wt%, and especially at least 40 wt%. The formulation can comprise less than 90 wt% or less than 80 wt% of zeolites having Y structure in total. Preferably, the formulation comprises 10 to 80 wt%, more preferably 20 to 60 wt% of zeolites having Y structure in total.

[0038] The formulation can be a liquid formulation or a solid formulation, for example a solid masterbatch. The formulation can comprise:

[0039] (i) zeolite Y; and

[0040] (ii) a carrier.

[0041] The zeolite Y is preferably dispersed in the carrier, preferably substantially uniformly dispersed in the carrier.

[0042] Preferably, unless otherwise stated herein, reference to "liquid" and "solid" refers to the state at 25°C and standard pressure (101325 Pa).

[0043] When the formulation is a liquid, the carrier is preferably a liquid. The carrier can have a boiling point at 760 mm Hg (according to ASTM D1078) of 150 to 1150°C, preferably 275°C to 1000°C or 275°C to 500°C. The carrier can have a viscosity (measured at 20°C using a Brookfield viscometer, spindle 2, 20 rpm) of 50 to 3500 cP, more preferably 200 to 1800 cP.

[0044] The carrier can comprise a hydrocarbon-containing liquid. The carrier can comprise one or more liquids, for example one or more hydrocarbon-containing liquids. The carrier can comprise a low molecular weight wax. The carrier can comprise a triglyceride. The carrier can comprise a liquid rubber. The carrier can comprise a mineral oil.

[0045] Examples of liquid rubbers include polyisobutylenes of low Mw (e.g. 1000 - 2500) and / or viscosity in the range 200 - 4750 cSt; polybutadienes (Mw 5000 - 10000); and ethylene-a-olefin copolymers (Mw 2700 - 16000). In general, the viscosity of the carrier is in the range 400 - 50000 cps.

[0046] When the carrier comprises one or more liquids, it can comprise one or more of the aforementioned carriers. For example, the carrier can comprise a mixture of a mineral oil (e.g. 10 to 30 wt%) and a polyisobutylene and / or liquid rubber (e.g. 70 to 90 wt%).

[0047] When the formulation is a solid, the carrier can comprise a polyolefin and / or a thermoplastic elastomer (TPE). The carrier can comprise a carrier typically used for solid masterbatches and / or a carrier that is compatible with the polymeric material in the first material, which can be in contact with the formulation. The carrier can comprise a polyolefin, such as polyethylene (e.g. HDPE or LDPE) or polypropylene, a styrene block polymer [such as styrene-ethylene-butylene-styrene (SEBS) or styrene-butadiene copolymer (SBC)], ethylene-vinyl acetate (EVA) or ethylene-propylene rubber (EPR).

[0048] The formulation (e.g. liquid or solid formulation) can comprise 10 to 90 wt%, preferably 30 to 80 wt%, of the carrier.

[0049] The sum of the wt% of all carriers in the formulation can be in the range of 10 to 90 wt%, preferably 30 to 80 wt%.

[0050] The sum of the wt% of all zeolites and all carriers in the formulation is suitably at least 50 wt%, preferably at least 70 wt%, more preferably at least 90 wt%, especially at least 95 wt%. The remainder can comprise other additives as described herein.

[0051] The formulation can comprise a colorant, which can be a pigment. The formulation can comprise a total of 0 to 50 wt% (e.g. 0 to 10 wt% or 0 to 5 wt%) of colorant. Colorant can be added to offset any discoloration of the formulation as described herein when added to a polymeric material.

[0052] The formulation can comprise an antioxidant / thermal stabilizer. The formulation can comprise an antioxidant, which can be a phenolic, a phosphite, a thioether or an organic sulphide. The formulation can comprise an antioxidant / free radical scavenger / anti-crosslinking agent selected from the group consisting of glutathione, thioctic acid, vitamins (e.g. ascorbic acid (vitamin C), vitamin B, vitamin D, vitamin E, tocopherol (synthetic or natural, a-, g-, d-), vitamin esters, water-soluble tocopherol derivatives, tocotrienol, water-soluble tocotrienol derivatives; melatonin, carotenoids, including carotenes, lutein, pycnogenol, glycosides, trehalose, polyphenols and flavonoids, quercetin, lycopene, lutein, selenium, nitric oxide, curcuminoids, 2-hydroxytetronic acid; cannabinoid, synthetic antioxidants such as t-butylhydroquinone, 6-amino-3-pyridinol, butylated hydroxyanisole, butylated hydroxytoluene, ethoxyquin, tannins, propyl gallate, other gallate esters, Aquanox TMThe formulation may include: families of Irganox® and Irganox® B (including Irganox® 1010, Irganox® 1076, Irganox® 1330, and Irganox® 1035); the Irgafos® family; phenolic compounds with different chain lengths and different numbers of OH groups; enzymes with antioxidant properties (e.g., superoxide dismutase); and herbal or plant extracts with antioxidant properties, such as St. John's wort, green tea extract, grape seed extract, rosemary, oregano extract, and mixtures, derivatives, analogs, or conjugated forms thereof. The formulation may contain antioxidants that are primary antioxidants with reactive OH or NH groups, such as hindered phenols or secondary aromatic amines; or secondary antioxidants, such as organophosphorus compounds or thiosynergists; or multifunctional antioxidants, hydroxylamines, or carbon-center free radical scavengers, such as lactones or acrylated bisphenols. Antioxidants may be selected individually or used in any combination. Antioxidants can be used in combination with hydroperoxide decomposers.

[0053] The formulation may contain a total of 0-10%, preferably 0-5%, more preferably 0-2% by weight of antioxidants / heat stabilizers.

[0054] When the formulation is a liquid, it may contain a viscosity control agent. The viscosity control agent may be a surfactant and / or fumed silica. The viscosity control agent may be a wax, silica, povidone, carbomer, poloxamer, carboxymethyl cellulose, hydroxyethyl cellulose, or polyacrylic acid. The formulation may contain 0 to 10% by weight, 0 to 5% by weight, or 0 to 1% by weight of the viscosity control agent.

[0055] In some cases, the formulation may contain one or more fillers (e.g., inorganic fillers, such as CaCO3). Preferably, the formulation contains less than 1% by weight, less than 0.5% by weight, or less than 0.1% by weight of filler, such as inorganic fillers.

[0056] When the formulation is configured to treat large quantities of polymer materials for automotive applications, it may contain anti-scratch additives, fillers, and / or light stabilizers.

[0057] When the formulation is a liquid formulation, it may contain 40 to 75% by weight of one or more liquid carriers (preferably a single liquid carrier), 25 to 60% by weight of zeolite Y, and 0 to 5% by weight of dispersant.

[0058] The preferred liquid formulation comprises 40 to 57% by weight of one or more liquid carriers (preferably a single liquid carrier), 40 to 50% by weight of zeolite Y, and 0 to 5% by weight of dispersant.

[0059] When the formulation is a solid formulation, it can comprise 40 to 75 wt% of one or more solid carriers (preferably a single solid carrier), 25 to 60 wt% of zeolite Y and 0 to 10 wt% of dispersant.

[0060] Preferably, the formulation is a liquid formulation. The liquid formulation can result in less colour shift (dL ) of the polymer introduced into the formulation compared to an equivalent solid formulation, as shown in Example 38.

[0061] In step (ii), the first material can be contacted with a formulation comprising the zeolite Y and / or a mixture can be obtained.

[0062] When a mixture is prepared in step (ii) or in a subsequent process, the mixture can comprise a polymeric material, a carrier and the zeolite Y. The polymeric material in the mixture can be acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl butyral (PVB), polyvinyl chloride (PVC), acrylonitrile-styrene-acrylate copolymer (ASA), polymethyl methacrylate (PMMA), polystyrene (PS) or polyolefin (PO). Preferably, it is a polyolefin.

[0063] The mixture can comprise polystyrene or one or more polyolefins. When the mixture comprises polystyrene, it preferably comprises at least two different sources and / or having different properties and / or performance of polystyrene. The polymeric material in the mixture preferably comprises recycled material, such as PCR or PIR. The polymeric material in the mixture can comprise 25 to 100 wt%, 25 to 75 wt% or 25 to 50 wt% of recycled polystyrene, such as PCR. The mixture can comprise virgin polymer, such as virgin polystyrene. The polymeric material in the mixture preferably comprises at least 25 wt% of virgin polymer. The polymeric material in the mixture can comprise 25 to 75 wt% or 50 to 75 wt% of virgin polymer. In some cases, such as for automotive applications described above, the polymeric material in the mixture can comprise up to 100 wt% of virgin polymer.

[0064] The mixture preferably comprises one or more polyolefins. Preferably, it comprises at least two polyolefins of different origin and / or having different properties and / or performance. The polymeric material in the mixture preferably comprises polyethylene. It can comprise 50 to 100 wt% polyethylene. The polymeric material in the mixture preferably comprises recycled material, such as PCR or PIR. It can comprise polyethylene PCR, in particular HDPE PCR. The polymeric material in the mixture preferably comprises at least 25 wt% recycled material, such as PCR. The polymeric material in the mixture can comprise 25 to 100 wt%, 25 to 75 wt% or 25 to 50 wt% recycled material, such as PCR. The polymeric material in the mixture can comprise up to 50 wt% polypropylene (PP), such as 10 to 50 wt% PP. The composition of the PCR can differ from each other. For example, the PCR can comprise inorganic contaminants and / or can be contaminated with fillers. For example, the PCR can comprise up to 3 wt% (such as 0.5 to 1 wt%) inorganic contaminants.

[0065] The mixture can comprise virgin polymers, such as virgin polyethylene, in particular virgin HDPE. The polymeric material in the mixture preferably comprises at least 25 wt% virgin polymers. The polymeric material in the mixture can comprise 25 to 75 wt% or 50 to 75 wt% virgin polymers.

[0066] The mixture can comprise a composition formed in the process; and / or can comprise a product produced in the process, which product can be in solid form, such as a molded article, a pellet or a granulate.

[0067] The mixture can comprise at least 90 wt%, preferably at least 94 wt%, more preferably at least 96 wt% polyolefins in total. It can comprise less than 99 wt% or less than 98 wt% polyolefins in total. The mixture can comprise at least 90 wt%, preferably at least 94 wt%, more preferably at least 96 wt% polyethylene in total. It can comprise less than 99 wt% or less than 98 wt% polyethylene in total. The remainder can comprise the zeolite Y.

[0068] The mixture can comprise at least 1000 ppm zeolite Y. It can comprise up to 50,000 ppm zeolite Y. Preferably, the mixture comprises 1000 to 30,000 ppm, more preferably 1000 to 20,000 ppm or 5000 to 20,000 ppm zeolite Y.

[0069] The mixture can comprise 0.1 wt%, preferably at least 0.2 wt%, of the zeolite Y. The mixture can comprise less than 5.0 wt% or less than 2.5 wt% of the zeolite Y. The mixture preferably comprises 0.1 to 5.0 wt%, more preferably 0.2 to 2.5 wt%, of the zeolite Y.

[0070] The total wt% of all zeolites in the mixture can be at least 0.1 wt%, preferably at least 0.2 wt%. The mixture can comprise less than 5.0 wt% or less than 2.5 wt% of zeolites in total. The mixture preferably comprises 0.1 to 5.0 wt%, more preferably 0.2 to 2.5 wt%, of zeolites in total.

[0071] The total wt% of all zeolites having the Y structure in the mixture can be at least 0.1 wt%, preferably at least 0.2 wt%. The mixture can comprise less than 5.0 wt% or less than 2.5 wt% of zeolites having the Y structure in total. The mixture preferably comprises 0.1 to 5.0 wt%, more preferably 0.2 to 2.5 wt%, of zeolites having the Y structure in total.

[0072] After step (ii), the method can comprise a step (iii) in which the first material and zeolite Y are melt processed, and / or the mixture as described above is melt processed. The melt processing can comprise extruding or injection moulding the first material and zeolite Y, for example to produce a moulded article, a pellet, a granule, a sheet or a film. Where pellets or granules are produced, these can subsequently be melt processed to produce an article.

[0073] In the method, the mixture can be produced after step (ii) and can be in the form of a product which can be separated, for example from the apparatus in which the product is produced. The product can comprise 50 to 99.9 wt% of the first polymeric material and 0 to 49.9 wt% of the recycled polymeric material. The product mass can comprise 50 to 79.9 wt% of the first polymeric material and 20 to 49.9 wt%, 25 to 49.9 wt% or 30 to 49.9 wt% of the recycled polymeric material. The remainder can comprise the zeolite Y. In one embodiment, the polymeric material in the product can comprise up to 100 wt% of recycled polymeric material, for example recycled polyolefin.

[0074] The product can be in the form of a granule or a pellet.

[0075] Alternatively, the product can be in the form of a moulded article, for example an article produced by extrusion (such as by extrusion blow moulding), compression moulding or injection moulding. The moulded article can be a packaging article, for example a receptacle or a container. The moulded article can be a packaging article, for example a receptacle or a container or a sheet.

[0076] The method of the first aspect can be used before or after a known process for treating recyclables to reduce malodorous substances (as described in the Background section herein). For example, the method of the first aspect can be used in conjunction with a thermal physical treatment (e.g. vacuum degassing or hot air / nitrogen stripping).

[0077] The method of the first aspect can comprise contacting the first material or a mixture comprising the first material and the zeolite Y with a second adsorbent, which can not be a zeolite Y and / or which can be a zeolite having complementary adsorption properties to the zeolite Y. Examples of second adsorbents include alumina and hydrotalcite.

[0078] In a particularly preferred embodiment, the second adsorbent can be a zinc compound. For example, it can be a zinc oxide or a zinc salt, such as a zinc salt of a carboxylic acid. Preferably, it is a zinc carboxylate. Preferably, it comprises a moiety of the following formula (preferably at least two, more preferably only two moieties):

[0079]

[0080] where O In relation to the zinc ion, R is an optionally substituted hydrocarbon chain, such as an optionally substituted alkyl or alkenyl group.

[0081] The group R can comprise 1 to 25 carbon atoms, such as 1 to 20 carbon atoms. The group R can be unsaturated, such as comprising one or more (preferably up to one) C=C moieties. When the group R is optionally substituted, it is optionally substituted with one or more (preferably only one) hydroxyl groups. The second adsorbent can be a bisalkanoyloxy zinc compound. The moiety of formula (I) can be a fatty acid residue.

[0082] Preferably, the second adsorbent is zinc ricinoleate.

[0083] When the method comprises contacting with a zeolite Y and the second adsorbent, the ratio defined by the weight percentage of zeolite Y divided by the weight percentage of second adsorbent introduced into the first material can be in the range 0.1 to 10.0, preferably in the range 0.3 to 3.0, more preferably in the range 0.5 to 2.0.

[0084] When the method uses the zeolite Y and a second adsorbent, the zeolite Y can be in a single preparation as described in step (ii), the second adsorbent can be in a separate preparation, which is used before, during or after step (ii). Preferably, however, the preparation used in step (ii) comprises the zeolite Y and the second adsorbent.

[0085] When the method comprises contacting with zeolite Y and the second adsorbent, the sum of the ppm values of zeolite Y and the second adsorbent in the first material, relative to the weight of the polymeric material, can be referred to as "SUM XX". SUM XX can be at least 1000 ppm. SUM XX can be at most 50,000 ppm. SUM XX can be in the range of 1000 to 30,000 ppm, more preferably 1000 to 20,000 ppm or 5000 to 20,000 ppm.

[0086] In the mixture prepared in the method step (ii), the sum of the wt% of zeolite Y and the second adsorbent (the sum referred to below as "SUM YY") can be at least 0.1 wt%, preferably at least 0.2 wt%. The SUM YY can be less than 5.0 wt% or less than 2.5 wt%. SUM YY can be in the range of 0.1 to 5.0 wt%, more preferably 0.2 to 2.5 wt%.

[0087] According to a second aspect of the application, there is provided the mixture itself as described in the first aspect. The mixture can be in the form of a product, for example a moulded article, a pellet or a granule, comprising a polymeric material and zeolite Y.

[0088] The zeolite Y can be as described in the first aspect.

[0089] The polymeric material preferably comprises one or more polystyrenes or one or more polyolefins. Preferably, it comprises at least two polyolefins of different origin and / or having different properties and / or performance. The polymeric material preferably comprises polyethylene. It can comprise 50 to 100 wt% polyethylene. The polymeric material preferably comprises a recycled material, for example PCR or PIR. It can comprise polyethylene PCR, especially HDPE PCR. The polymeric material preferably comprises at least 25 wt% of a recycled material, for example PCR. The polymeric material can comprise 25 to 100 wt%, 25 to 75 wt% or 25 to 50 wt% of a recycled material, for example PCR. The polymeric material can comprise up to 50 wt% polypropylene (PP), for example 10 to 50 wt% PP.

[0090] The polymeric material can comprise virgin polymers, for example virgin polyethylene, especially virgin HDPE. The polymeric material preferably comprises at least 25 wt% of virgin polymers. The polymeric material in the mixture can comprise 25 to 75 wt% or 50 to 75 wt% of virgin polymers.

[0091] The polymeric material can include at least 90 wt%, preferably at least 94 wt%, more preferably at least 96 wt% polyolefin in total. It can include less than 99 wt% or less than 98 wt% polyolefin in total. The polymeric material can include at least 90 wt%, preferably at least 94 wt%, more preferably at least 96 wt% polyethylene in total. It can include less than 99 wt% or less than 98 wt% polyethylene in total.

[0092] The mixture can include 0.1 wt%, preferably at least 0.2 wt% of the zeolite Y. The mixture can include less than 5.0 wt% or less than 2.5 wt% of the zeolite Y. The mixture preferably includes 0.1 to 5.0 wt%, more preferably 0.2 to 2.5 wt% of the zeolite Y.

[0093] The sum of the wt% of all zeolites in the mixture can be at least 0.1 wt%, preferably at least 0.2 wt%. The mixture can include less than 5.0 wt% or less than 2.5 wt% of zeolites in total. The mixture preferably includes 0.1 to 5.0 wt%, more preferably 0.2 to 2.5 wt% of zeolites in total.

[0094] The sum of the wt% of all zeolites having the Y structure in the mixture can be at least 0.1 wt%, preferably at least 0.2 wt%. The mixture can include less than 5.0 wt% or less than 2.5 wt% of zeolites having the Y structure in total. The mixture preferably includes 0.1 to 5.0 wt%, more preferably 0.2 to 2.5 wt% of zeolites having the Y structure in total.

[0095] The mixture can include zeolite Y and a second adsorbent, wherein the zeolite Y and the second adsorbent independently have any of the features of the zeolite Y and the second adsorbent of the first aspect. When the mixture includes zeolite Y and the second adsorbent, the sum of the ppm values of the zeolite Y and the second adsorbent in the mixture relative to the weight of the polymeric material can be referred to as “SUM XX”. SUM XX can be at least 1000 ppm. SUM XX can be at most 50,000 ppm. SUM XX can be in the range of 1000 to 30,000 ppm, more preferably 1000 to 20,000 ppm or 5000 to 20,000 ppm.

[0096] The sum of the wt% of the zeolite Y and the second adsorbent in the mixture (the sum referred to below as “SUM YY”) can be at least 0.1 wt%, preferably at least 0.2 wt%. The SUM YY can be less than 5.0 wt% or less than 2.5 wt%. SUM YY can be 0.1 to 5.0 wt%, more preferably 0.2 to 2.5 wt%.

[0097] According to a third aspect of the application, there is provided the formulation as defined in the first aspect per se.

[0098] The formulation can be a liquid formulation or a solid formulation, for example a solid masterbatch. The formulation can comprise:

[0099] (i) zeolite Y; and

[0100] (ii) a carrier.

[0101] The formulation can comprise at least 10 wt%, preferably at least 20 wt%, more preferably at least 30 wt%, especially preferably at least 40 wt% of the zeolite Y. The formulation can comprise less than 90 wt% or less than 80 wt% of the zeolite Y. The formulation preferably comprises 10 to 80 wt%, more preferably 20 to 60 wt% of the zeolite Y.

[0102] The total wt% of all zeolites in the formulation can be at least 10 wt%, preferably at least 20 wt%, more preferably at least 30 wt%, especially at least 40 wt%. The formulation can comprise less than 90 wt% or less than 80 wt% of zeolites in total. Preferably, the formulation comprises 10 to 80 wt%, more preferably 20 to 60 wt% of zeolites in total.

[0103] The total wt% of all zeolites having the Y structure in the formulation can be at least 10 wt%, preferably at least 20 wt%, more preferably at least 30 wt%, especially at least 40 wt%. The formulation can comprise less than 90 wt% or less than 80 wt% of zeolites having the Y structure in total. Preferably, the formulation comprises 10 to 80 wt%, more preferably 20 to 60 wt% of zeolites having the Y structure in total.

[0104] The zeolite Y is preferably dispersed in the carrier, preferably substantially uniformly dispersed in the carrier.

[0105] When the formulation is a liquid, the carrier is preferably a liquid. The carrier can have a boiling point (according to ASTM D1078) of 150 to 1150 °C, preferably 275 °C to 1000 °C or 275 °C to 500 °C at 760 mm Hg. The carrier can have a viscosity (measured at 20 °C using a Brookfield viscometer, spindle 2, 20 rpm) of 50 to 3500 cP, more preferably 200 to 1800 cP.

[0106] The carrier can comprise a hydrocarbon-containing liquid. The carrier can comprise one or more liquids, for example one or more hydrocarbon-containing liquids. The carrier can comprise a low molecular weight wax. The carrier can comprise a triglyceride. The carrier can comprise a liquid rubber. The carrier can comprise a mineral oil.

[0107] Examples of liquid rubbers include polyisobutylenes of low Mw (e.g. 1000-2500) and / or viscosity in the range 200-4750 cSt; polybutadienes (Mw 5000-10000); and ethylene-a-olefin copolymers (Mw 2700-16000). Generally, the viscosity of the carrier ranges from 400-50000 cps.

[0108] When the carrier comprises one or more liquids, it can comprise one or more of the aforementioned carriers. For example, the carrier can comprise a mixture of mineral oil (e.g. 10 to 30 wt%) and polyisobutylene and / or liquid rubber (e.g. 70 to 90 wt%).

[0109] When the formulation is a solid, the carrier can comprise a polyolefin and / or a thermoplastic elastomer (TPE). The carrier can comprise a carrier typically used for solid masterbatches. The carrier can comprise a polyolefin, such as polyethylene (e.g. HDPE or LDPE) or polypropylene, a styrene block polymer [e.g. styrene-ethylene-butylene-styrene (SEBS) or styrene-butadiene copolymer (SBC)], ethylene-vinyl acetate (EVA) or ethylene-propylene rubber (EPR).

[0110] The formulation can comprise 10 to 90 wt%, preferably 30 to 80 wt%, of the carrier.

[0111] The sum of the wt% of all carriers in the formulation can be in the range 10 to 90 wt%, preferably 30 to 80 wt%.

[0112] In the formulation, the sum of the wt% of all zeolites and all carriers is suitably at least 50 wt%, preferably at least 70 wt%, more preferably at least 90 wt%, especially at least 95 wt%. The remainder can comprise other additives as described herein.

[0113] The formulation can comprise a colourant, which can be a pigment. The formulation can comprise a total of 0 to 50 wt% (e.g. 0 to 10 wt% or 0 to 5 wt%) of colourant. Colourant can be added to offset any colour change of the formulation when added to a polymeric material as described herein.

[0114] The formulation can comprise an antioxidant / heat stabiliser, such as described in the first aspect.

[0115] The formulation can comprise a total of 0-10%, preferably 0-5%, more preferably 0-2 wt% of antioxidant / heat stabiliser.

[0116] When the formulation is a liquid, the formulation can comprise a viscosity control agent. The viscosity control agent can be a surfactant and / or fumed silica. The viscosity control agent can be a wax, a silica, povidone, carbomer, poloxamer, carboxymethylcellulose, hydroxyethylcellulose or polyacrylic acid. The formulation can comprise 0 to 10 wt%, 0 to 5 wt% or 0 to 3 wt% of a viscosity control agent.

[0117] In some cases, the formulation can comprise one or more fillers (e.g. inorganic fillers such as CaCCb). Preferably, the formulation comprises less than 1 wt%, less than 0.5 wt% or less than 0.1 wt% of a filler, e.g. an inorganic filler.

[0118] In some cases, the formulation can comprise a zeolite Y as described in the first aspect or the second aspect and a second adsorbent. In this case, the ratio defined by the weight percentage of zeolite Y divided by the weight percentage of the second adsorbent introduced in the formulation can range from 0.1 to 10.0, preferably from 0.3 to 3.0, more preferably from 0.5 to 2.0.

[0119] When the formulation comprises both a zeolite Y and a second adsorbent, the sum of the weight percentages of the zeolite Y and the second adsorbent in the formulation can be referred to as "SUM QQ". In the formulation, SUM QQ can be at least 10 wt%, preferably at least 20 wt%, more preferably at least 30 wt%, especially at least 40 wt%. In the formulation, SUM QQ can be less than 90 wt% or less than 80 wt%. SUM QQ can be from 10 to 80 wt%, more preferably from 20 to 60 wt%.

[0120] In preferred embodiments, when the formulation comprises both a zeolite Y and a second adsorbent, the second adsorbent can be a zinc compound as described in the first aspect.

[0121] The second adsorbent can be a bisalkanoyloxy zinc compound. Preferably, the second adsorbent is zinc ricinoleate.

[0122] Any feature of any aspect of any of the inventions described herein can be combined with any other feature of any other invention described herein mutatis mutandis.

[0123] A specific embodiment of the invention will now be described, by way of example only, with reference to the accompanying drawings in which:

[0124] Figure 1 The % reduction in the content of specific materials in Comparative Examples C1 to C11 is shown in detail;

[0125] Figure 2The % reduction in the content of specific substances in Examples 7 to 11 and C14 to C16 is shown in detail;

[0126] Figure 3 The % reduction in the content of specific substances in Examples 14 to 20 is shown in detail; and Figure 4 The plots of zeolite Q1 concentration vs. brightness / darkness (dL ) for liquid dispersions and solid masterbatches.

[0127] The following materials are referred to herein.

[0128] Versalis Eraclene BC 82 - refers to a high density polyethylene resin (HDPE).

[0129] Spiked HDPE resin - refers to a HDPE resin spiked with a mixture of odour substances having different classes of chemical functionality (e.g. acids, aldehydes and / or ketones) that are commonly found in commercial grade PCR. The resin was prepared by extrusion moulding a base virgin HDPE resin (Versalis Eraclene BC 82) to which was added a mixture comprising hexanal, octanal, 1-hexanol, 2-hexanone, dodecane, methyl hexanoate, glycol butyl ether, hexanoic acid, nonanoic acid, limonene, linalool and eugenol.

[0130] Real world PCR - refers to a HDPE recycled grade that is currently available on the European market. PCR grades can vary greatly in terms of melt flow rate, polypropylene content and inorganic content. The following table shows typical ranges for these PCR properties:

[0131]

[0132] When a real world PCR is used in any of the embodiments described herein, it is blended with Versalis Eraclene BC 82 in a 1 : 1 weight ratio. This is higher than the ratio currently used commercially - due to the off-notes of real world PCR in the absence of a satisfactory adsorbent, virgin resin is typically blended with around 25wt% of PCR.

[0133] The following are sold as general adsorbents.

[0134]

[0135] The following are referred to herein:

[0136]

[0137] The following other materials are also referred to herein:

[0138]

[0139] Unless otherwise stated, reference to “ppm” means “parts per million” (by weight) of one material to another.

[0140] Reference is made herein to the following evaluations:

[0141] Evaluation #1 - Evaluation of resin volatile emissions

[0142] Unless otherwise stated herein, the thermal desorption gas chromatography (TD-GC-MS) standard analytical test protocol was employed to evaluate volatile emissions from spiked odor resin and real world PCR. This was used to understand the overall and specific emissions of the materials and to demonstrate the effectiveness of the protocol. The key parameters of the TD-GC-MS analytical method are shown below:

[0143] TD Conditions:

[0144] Instrument: Markes International TD100-xr™

[0145] Desorption temperature: 110 °C;

[0146] Desorption time: 30 minutes

[0147] Focusing trap: Air Toxin (Markes International Part No. U-T3ATX-2S)

[0148] Focusing trap temperature: -30 °C

[0149] Trap desorption temperature: 290 °C

[0150] Focusing trap desorption time: 5 minutes;

[0151] GC Conditions:

[0152] Instrument: Thermofisher Scientific Trace 1310 GC

[0153] Chromatographic column: Thermofisher Scientific TG-5MS, 60 m x 0.25 mm x 0.25 pm

[0154] Carrier: Helium

[0155] Carrier gas flow: 1.5 mL / min (constant flow)

[0156] Oven program: 80 °C (5 minutes), ramp to 250 °C at 3 °C / min, hold for 10 minutes

[0157] Quadrupole MS conditions:

[0158] Instrument: Thermofisher Scientific TSQ 9000-AEI

[0159] Transfer line: 250 °C

[0160] Ion source: 250 °C

[0161] Mass range: m / z 45 - 300

[0162] Scan time: 0.2 seconds

[0163] Evaluation #2 - Assessment of resin odour intensity

[0164] The odour intensity of selected resins was evaluated using a method based on VDA 270 (Determination of the odour characteristics of interior trim materials for motor vehicles). In this evaluation, a sensory panel of four participants assessed the odour intensity of each sample and scored according to the following odour intensity scale.

[0165]

[0166] The samples for evaluation were prepared by weighing 40 g of pellets in a 180 mL container and capping each container. The containers were left at room temperature. Each participant uncapped the container, assessed the odour in the headspace of the jar and scored. The results were reported in average intensity scale.

[0167] Example 1 - General procedure for preparing liquid formulations of candidate odour-reducing materials

[0168] Liquid formulations in dispersion were prepared by mixing the candidate odour-reducing material with a liquid carrier, optionally in the presence of a dispersant. The material can be added gradually and mixed with the carrier and optional dispersant (using a high speed disperser for one minute at 1000-3000 rpm), followed by a final mixing at 3000 rpm for at least 5 minutes.

[0169] The liquid formulation can comprise up to 50% by weight of the candidate odour-reducing material, up to 5% by weight of the dispersant, and the remainder being a liquid carrier. The carrier is suitably well soluble in the added polymer. It can be selected from: white mineral oil, CAS 8042-47-5, petroleum distillate, CAS 64741-89-5, hydrotreated distillate, CAS 64742-47-8, ethoxysorbitol trioleate, CAS 9005-70-3, sorbitol trioleate, CAS 26266-58-0, rapeseed oil, CAS 68956-68-3.

[0170] The dispersant can be selected from: polymeric hyperdispersants, including polymeric hyperdispersants with amine anchors and polymeric hyperdispersants with acid anchors.

[0171] Example 2 - General procedure for preparing candidate deodorising material solid formulations

[0172] The solid formulation in the form of a masterbatch can be prepared by extruding a mixture of solid carrier, candidate deodorising material and optional dispersant, followed by pelletisation. The solid formulation can comprise up to 50wt% of candidate deodorising material, up to 5wt% of dispersant, with the remainder being carrier resin. The carrier resin can be selected from LDPE, HDPE, for example Versalis Eraclene BC 82 or similar carrier resin. The dispersant can be a polyethylene wax.

[0173] Example 3 - Production of pellets containing spiked odour resin or real world PCR and deodorising material formulations by feed throat addition (first method) General procedure for PCR and deodorising material formulation pellets

[0174] To a container, resin pellets are weighed, then the candidate deodorising material raw material or liquid dispersion of candidate deodorising material (as described in Example 1) is weighed on to the pellets at the predetermined dosage weight %. The container is sealed and shaken in a vibrating mixer to ensure homogeneity. This mixture is then poured into the extruder hopper and fed at a set rate into the extruder feed throat of a Rondol twin screw extruder. Pellets comprising spiked odour resin or real world PCR and deodorising material formulation are produced for subsequent evaluation.

[0175] The same method can also be used for the solid formulation of Example 2.

[0176] Suitably, in a preferred embodiment, the Example 1 formulation is used with a deodorising material loading of 45wt%. This deodorising material is found to disperse well in the resin with negligible impact on it.

[0177] Example 4 - Production of pellets containing spiked odour resin or real world PCR and deodorising material formulations by melt injection (second method) General procedure for PCR and deodorising material formulation pellets

[0178] This involves injecting a liquid dispersion of candidate deodorising material as described in Example 1 via a port on the Khune single screw extruder (38mm) barrel, to mix directly with the molten resin within the screw. This is then processed through a strand die and pelletiser, to produce pellets.

[0179] Example 5 - Analysis of pellets to assess effectiveness of odour substance reduction levels

[0180] According to Assessment #1, the pellets are analyzed by TD-GC-MS to isolate and quantify the concentrations of odorants present in the pellets. In reporting the results, the amount of odorants in the pellets containing the candidate deodorizing material is compared to an appropriate control group containing the same resin, except that any candidate deodorizing material being evaluated is omitted. The % reduction in odorants present compared to the control group can then be calculated. In addition, to aid in comparison, the sum of all terpinene-related substances is determined as "Total Terpinenes" and referred to herein as "TTC Reduction." This indicates that some candidate deodorizing materials can isomerize odorants, which does not reduce the overall concentration.

[0181] Example 6 - Effectiveness of candidate deodorising materials.

[0182] Following the procedure described in Example 5, the deodorizing performance of a series of adsorbents was evaluated when incorporated into spiked HDPE using the liquid formulation described in Example 3.

[0183] The following table details the name and ppm of adsorbents in the HDPE pellets produced.

[0184]

[0185] Figure 1 The % reduction in the content of specific substances is detailed. Figure 1 In some of Examples CI - C11, no reduction in the content of certain specific substances was measured. Overall, Figure 1 It is shown that even at relatively high levels of additive, known adsorbents provide only limited benefit.

[0186] Examples 7 to 11 and C14 to C16 - Comparison of preferred deodorising materials with candidate adsorbents

[0187] Following the procedure described in Example 5, the deodorizing performance of zeolite Q1 (previously determined to be a favorable deodorizing material) was evaluated against a number of known adsorbents and incorporated into spiked HDPE as described in Example 3.

[0188] The following table details the name and ppm of adsorbents in the HDPE pellets produced as described in Example 5.

[0189]

[0190] Figure 2The % reduction in specific material content (limonene reduction, eugenol reduction, linalool reduction, and TTC reduction) is shown in detail and indicates that zeolite Ql has high efficiency at relatively low concentrations, significantly reducing the content of key odorants. In the case of zeolites P2 and P5, the total terpinolene concentration is not reduced, but there is a reduction in limonene, eugenol, and linalool. This indicates that when zeolite P2 is used, limonene, eugenol, and linalool are converted to other terpinolene species that still have an odor response, while with zeolite Ql, these same odorants are removed or further converted to species that do not have an odor response (i.e., non-terpinolene species). This can indicate that the action of zeolite Ql is to convert certain odorants to species with a lower odor response (or no odor response) or to remove them completely from the polymer matrix.

[0191] Example 12 and Comparative Examples C17-C20 - Performance comparison of zeolite Q1 with other candidate adsorbents for a range of odour substances Example 13 and Comparative Examples C21 to C23 - Deodorisation in real world PCR

[0192] A series of known adsorbents (incorporated into spiked HDPE as described in Example 3) were evaluated for deodorizing performance according to the procedure described in Example 5. The following table shows the odorants evaluated in detail, as well as the results for zeolite Ql and other adsorbents (zeolite P4, kaolin, a masterbatch containing zinc ricinoleate, and other adsorbents, and bentonite) at a specific addition level (ppm relative to the spiked HDPE resin).

[0193]

[0194] Examples 14 to 20 - Performance evaluation of combinations of zeolite Q1 with other known adsorbents

[0195] A variety of odorants, including various organic, inorganic, and polymeric contaminants, were found in commercially available HDPE PCR. A series of candidate adsorbents were evaluated for deodorizing performance according to the procedure described in Example 5, each at a level of 5000 ppm in the HDPE PCR, for their ability to reduce the concentration of various odorants and / or contaminants, with the results shown in the following table. The % reduction is shown in detail, with more negative values indicating greater reduction. If the % reduction for a specific material is positive, this indicates that one or more other materials have been converted to the specific material. Concentrations were determined using the 2-methylheptane semi-quantitative method.

[0196]

[0197]

[0198] It is noted from the above table that Example 13 provides superior performance compared to the comparative examples.

[0199] Figure 3

[0200] The deodorizing performance of combinations of zeolite Ql with other adsorbents (referred to as "second adsorbents") was evaluated following the procedure described in Example 5. The table below details the name and ppm of each second adsorbent that was introduced into spiked HDPE along with 1000 ppm of zeolite Ql. Zeolite Ql was added as described in Example 3, while the second adsorbent was added as a dry powder along with the zeolite Ql.

[0201]

[0202] Examples 21 to 24 - Performance evaluation of combinations of zeolite Q1 with other known adsorbents in real world PCR The results are shown, indicating that the performance of this combination was outstanding. It appears that the second adsorbent is complementary and / or synergistic with zeolite Ql.

[0203] Examples 25 to 31 and C24 to C40 - Performance of a range of zeolite materials in reducing key odour substances

[0204] The performance of combinations of zeolite Ql (at two different levels) with adsorbents alumina or hydrotalcite was evaluated in real-world PCR following the procedure described in Examples 14-20. The results are shown in the table below, which details the % reduction in each case, with more negative values indicating greater reduction. If the % reduction for a particular species is positive, it indicates that one or more other species has been converted to that particular species.

[0205]

[0206]

[0207] The overall results show the excellent performance of the examples, significantly reducing the levels of multiple colored species in real-world PCR.

[0208] Analysis Examples 32 to 37 - Deodorisation in real world "problem" PCR.

[0209] HDPE polymers were spiked with appropriate concentrations of key odor species (listed in the table below):

[0210]

[0211] A series of candidate deodorizing materials, including zeolites and other materials, were evaluated for deodorizing performance following the procedure described in Example 5, added as a liquid formulation or as a dry powder at the specified loading.

[0212] The table below provides information about the materials evaluated and the results obtained, including the % reduction obtained for each additive.

[0213]

[0214] The results show that the materials of Examples 25 to 31 (all Y zeolites) are more effective at reducing the odour material content than the other candidate deodorising materials.

[0215] Example 38 - Comparison of adsorbent-containing liquid dispersions with adsorbent-containing solid masterbatches.

[0216] Some commercially available PCR grades (referred to as PCR1 and PCR2) were found to be "problematic" in that the deodorising effect using a single deodorising material was less than optimum. As described below, such PCR's were treated with a 1 :1 weight ratio of zeolite Q1 and zinc ricinoleate.

[0217] The PCR's can be treated with zeolite Q1 as described in Example 3. Zinc ricinoleate is added as a dry powder as described in Examples 14 to 20. The treated samples are assessed as described in Assessment #2 and compared to other examples as shown in the table below.

[0218]

[0219] It will be noted from the above table that the addition of zinc ricinoleate significantly improves (i.e. reduces) the intensity rating (see Examples 34 and 37 and compare to other examples). The rating achieved is found to be acceptable for automotive interior applications (which require an intensity rating of < 2.5).

[0220] Figure 4

[0221] A solid masterbatch comprising zeolite Q1 was prepared by extrusion with a LDPE polymer carrier to give a masterbatch with an active loading of 45 wt% following the general procedure described in Example 2.

[0222] A liquid formulation comprising zeolite Q1 was prepared with an active loading of 45 wt% following the general procedure described in Example 1.

[0223] Plate samples were prepared by injection moulding Eraclene HDPE virgin polymer and adding the liquid formulation to give three active levels (1000, 2500 and 5000 ppm). Comparative plate samples were prepared by injection moulding Eraclene HDPE virgin polymer and adding the masterbatch to give three active levels (1000, 2500 and 5000 ppm).

[0224] The colour of the plates was measured using a Minolta CM-3600-A spectrophotometer and the results are shown in Table 6. Example 39 - Identification of specific zeolites in polymeric compositions These results clearly show that the colour shift is significantly greater (and therefore less favourable) when using a masterbatch containing the adsorbent compared to using a liquid formulation to add the adsorbent.

[0225] ​

[0226] In some cases, it can be desirable to identify the presence and / or class of zeolite in a polymer composition. This can be done as follows:

[0227] The polymer pellets (or any available form of polymer containing suspected zeolite) are ashed in a large crucible at 550 °C for about 1 hour. The diffraction pattern of the zeolite and ash samples are then collected using a Rigaku Miniflex™ over a range of 2 theta = 3° to 90°. The 1-D integrated diffraction pattern is peak fitted and compared to a database of diffraction patterns in the software provided by the manufacturer to identify if a zeolite is present.

[0228] The present application is not limited to the details of the foregoing embodiments. The present application extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any method or process step so disclosed.

Claims

1. A method for processing a large quantity of polymer material, the method comprising: (i) Select a first material containing polymer materials; and (ii) Contact the first material with zeolite Y.

2. The method of claim 1, wherein the Si:Al molar ratio of the zeolite Y is at least 3.0 (preferably at least 5.0); and / or the molar ratio is in the range of 5.0:1 to 100:

1.

3. The method of claim 1 or claim 2, wherein the counter ion of zeolite Y is selected from H + Na + and NH4 + .

4. The method as described in any of the preceding claims, wherein the surface area of ​​the zeolite Y is at least 410 m². 2 / g (preferably at least 700m) 2 / g).

5. The method as described in any one of the preceding claims, wherein the method is a method for treating a large quantity of polymer material to reduce its odor.

6. The method as claimed in any of the preceding claims, wherein the method comprises processing a first material comprising recycled polymer material.

7. The method of claim 6, wherein the recycled polymer material is recycled polystyrene or recycled polyolefin.

8. The method of any of the preceding claims, wherein the first material comprises at least 90% by weight (or at least 99% by weight) of a recycled polymer material, such as recycled polyolefin.

9. The method of any one of claims 6 to 8, wherein the recycled polymer material comprises at least 90% by weight (preferably at least 99% by weight) polyethylene or at least 90% by weight (preferably at least 99% by weight) polypropylene.

10. The method of any of the preceding claims, wherein pellets doped with the zeolite are prepared.

11. The method of any of the preceding claims, wherein the first material comprises a first polymer material and a recycled polymer material, wherein the first polymer material comprises at least 80% by weight of virgin polystyrene or virgin polyolefin, and the first material comprises 20 to 80% by weight of the first polymer material and 20 to 80% by weight of the recycled polymer material.

12. The method as claimed in any of the preceding claims, wherein a formulation comprising the zeolite Y is used in step (ii), wherein the formulation comprises 10 to 80% by weight (preferably 20 to 60% by weight) of the zeolite Y.

13. The method of claim 12, wherein the formulation comprises a total of 10 to 80% by weight (preferably 20 to 60% by weight) of zeolite; and / or the total weight percentage of all zeolites having a Y structure in the formulation is at least 10% by weight and less than 80% by weight.

14. The method of claim 12 or claim 13, wherein the formulation comprises: (i) Zeolite Y; and (ii) Carrier.

15. The method of claim 14, wherein: The formulation comprises 10 to 90% by weight (preferably 30 to 80% by weight) of the carrier; and / or The total weight percentage of all carriers in the formulation is in the range of 10 to 90% by weight (preferably 30 to 80% by weight); and / or The total weight percentage of all zeolites and all carriers in the formulation is at least 50% by weight (preferably at least 95% by weight).

16. The method of any one of claims 12 to 15, wherein the liquid formulation comprises 47 to 57% by weight of one or more liquid carriers, 40 to 50% by weight of zeolite Y and 0 to 5% by weight of dispersant.

17. The method as described in any of the preceding claims, wherein, In step (ii), the first material is contacted with a formulation containing the zeolite Y to generate a mixture, wherein the polymer material in the mixture comprises 25 to 100% by weight of recycled material; and, optionally, the polymer material in the mixture comprises 25 to 75% by weight of virgin polymer.

18. The method of claim 17, wherein the mixture comprises 1,000 to 30,000 ppm (preferably 5,000 to 20,000 ppm) of zeolite Y.

19. The method of claim 17 or 18, wherein, In the method, the mixture generated after step (ii) is in product form, the product being separated from the apparatus for preparing the product, wherein the product is in pellet or granule form, or in the form of a molded article.

20. The method of claim 19, wherein the molded article is a reservoir or container or a sheet.

21. The method as described in any of the preceding claims, wherein the method is used in conjunction with a thermophysical treatment, such as vacuum degassing or hot air / nitrogen stripping.

22. The method of any of the preceding claims, the method comprising contacting the first material or a mixture comprising the first material and the zeolite Y with a second adsorbent, the second adsorbent being not zeolite Y, and / or being a zeolite having adsorption properties complementary to those of the zeolite Y.

23. The method of claim 22, wherein the second adsorbent is a zinc compound, such as a zinc salt of a carboxylic acid.

24. The method of claim 22 or claim 23, wherein the second adsorbent is a zinc dialkyloxy group compound, preferably zinc ricinoleate.

25. A mixture in the form of a product, such as a molded article, pellets, or granules, wherein the mixture comprises a polymeric material and zeolite Y.

26. The mixture of claim 25, wherein the zeolite Y is as described in any one of claims 1 to 24, and the polymer material comprises one or more polystyrene or one or more polyolefins.

27. The mixture of claim 25 or claim 26, wherein the polymer material comprises 25 to 100% by weight of recycled material.

28. The mixture of any one of claims 25 to 27, wherein the polymeric material in the mixture comprises at least 25% by weight of a virgin polymer, such as a virgin polyolefin.

29. The mixture according to any one of claims 25 to 28, wherein: The polymer material comprises at least 90% by weight of polyolefin; and / or The mixture contains 0.1 to 5.0% by weight of the zeolite Y.

30. The mixture of any one of claims 25 to 29, wherein the mixture comprises zeolite Y and a second adsorbent, wherein the second adsorbent is a zinc compound, such as a zinc salt of a carboxylic acid, and optionally zinc ricinoleate.

31. The mixture of claim 30, wherein: The sum of the ppm values ​​of zeolite Y and the second adsorbent relative to the weight of the polymer material in the mixture is referred to as "SUM XX", wherein SUM XX is at least 1000 ppm and can be in the range of 1000 to 30,000 ppm, preferably 5000 to 20,000 ppm; and / or The total weight percentage of zeolite Y and the second adsorbent in the mixture (referred to as "SUM YY") is at least 0.1% by weight, and may be in the range of 0.1% to 5.0% by weight, preferably 0.2% to 2.5% by weight.

32. A formulation for use in the method of any one of claims 1 to 24 and / or a formulation incorporated into a mixture of any one of claims 25 to 31, the formulation comprising: (i) Zeolite Y; and (ii) Carrier.

33. The formulation of claim 32, wherein: The formulation comprises 10 to 80% by weight (preferably 20 to 60% by weight) of the zeolite Y; and / or The formulation contains a total of 10 to 80% by weight (preferably 20 to 60% by weight) zeolite; The formulation comprises 10 to 90% by weight (preferably 30 to 80% by weight) of the carrier; and / or The total weight percentage of all carriers in the formulation is in the range of 10 to 90% by weight (preferably 30 to 80% by weight); and / or The total weight percentage of all zeolites and all carriers in the formulation is at least 50% by weight (preferably at least 95% by weight).

34. The formulation of claim 32 or claim 33, wherein the formulation comprises zeolite Y and a second adsorbent, wherein: In the formulation, the ratio defined by dividing the weight percentage of zeolite Y by the weight percentage of the second adsorbent is in the range of 0.1 to 10.0, preferably in the range of 0.5 to 2.0; The total weight percentage of zeolite Y and the second adsorbent in the formulation is referred to as "SUM QQ", wherein SUM QQ is at least 10% by weight and optionally in the range of 10 to 80% by weight or 20 to 60% by weight.

35. The formulation of claim 34, wherein the second adsorbent is a zinc compound as described in claim 23 or 24; and the second adsorbent is optionally a zinc dialkyl oxychloride compound and / or zinc ricinoleate.

36. The formulation of any one of claims 32 to 35, wherein the formulation is a liquid, and the carrier has a boiling point in the range of 275°C to 500°C at 760 mm Hg according to ASTM D1078, and a viscosity in the range of 50-3500 cP as measured using a Brookfield viscometer, rotor 2, 20 rpm, 20°C.

37. The formulation of any one of claims 32 to 36, wherein the carrier comprises a low molecular weight wax, triglyceride, liquid rubber, or mineral oil.

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