WO2007068656A1

WO2007068656A1 - A method of transforming a recycled polyolefin into a performance enhanced polymeric material

Info

Publication number: WO2007068656A1
Application number: PCT/EP2006/069452
Authority: WO
Inventors: Andrew Burns; Alec Milligan; Robert Meek; Maura Burke
Original assignee: Crownstone Limited
Priority date: 2005-12-12
Filing date: 2006-12-07
Publication date: 2007-06-21
Also published as: EP1960460A1; IE20060896A1; IES20060895A2

Abstract

A method of transforming a recycled polyolefin into a performance enhanced polymeric material is disclosed. The invention also related to a performance enhanced polymeric material prepared by that method. The polymeric material can comprise up to 99% recycled polyolefin by weight of the material and also comprises a modified nanoclay. The resultant performance enhanced polymeric material has improved properties sucn as modulus of stiffness, tensile strength, tensile modulus and stress crack resistance.

Description

"A method of transforming a recycled polyolefϊn Into a performance enhanced polymeric material"

Introduction

The present invention relates to a method of transforming a recycled polyolefin into a performance enhanced polymeric material and further relates to a performance enhanced polymeria material prepared by that method.

An ever increasing amount of polyolefin waste is produced worldwide each year. Recycling is one way of dealing wilh this waste, A polyolefin is a polymer of the alkene family of hydrocarbons. One of the major problems with recyded polyolefins is that they have reduced physical properties, in particular impact resistance, slress crack resistance and stiffness compared to virgin polyolefins. As recycled polyolefins have inherently lower performance ineir use in further applications generally is limited to low value applications. Additionally, as the cost of recycling polyolefins is high, the recycling cost can more often that not outweigh the value of the resultant recycled polyolefin.

During the initial use of the polyolefin, UV light and oxygen present cars break the carbon bonds within the polymeric chains thus reducing the overall molecular weight of the polyotefins. As the molecular weight of the polyolefins is reduced this causes an overall reduction in physical properties. Additionally, stress of the polyolefins during use will cause "creep" of the polymeric molecules. "Creep" is defined as pulling Ihe amorphous or crystalline regions of the polymeric chains apart. This leads to a reduction in the modulus and impact strength of the polyolefins.

The recycling process itself can be quite complicated and costly and generally involves at feast mechanical recycling of the polyolefins. During recycling, reprocessing of the polyolefin waste requires a heat processing step, thereby leading to further degradation of the properties of ϊhe polyolefins and making repeat use for Ihe same application difficult. After heat processing, the polyolefins are fecompounded to reform the crystalline and amorphous regions of the polymeric chains. However, due to the polymeric chain scission which occurs during the initial use of the polyolefin, the polymeric chains cannot reform completely resulting in a reduction in the moϊeeular weight of the polyαlefms compared wilh virgin polyolefins. This results in a concomitant reduction in the physical properties of the recycled polyolefins and thus limits the use of these recycled polyotefins to low value applications.

There is therefore a need for a method of transforming recycled polyolefins into a performance enhanced polymeric material which can be used in high value applications.

Statements of Invention

According to the invention, there is provided a method of transforming a recycled polyolefin into a performance enhanced polymeric material;

characterised in that;

the method comprises mining a modified nanoclay wilh the recycled polyolefin to form a clay-polyolefin mix, and

extruding ihe clay-polyolefin mix to form the performance enhanced polymeric material.

The advantage of this method is that it uses a low value recycled polyolefin to provide a high value product. The recycled polyoSefjn is considered to be low value as it has reduced physical properties and is applications are thus limited. By converting this low value product into a performance enhanced polymeric material, the range of applications for which it is suitable is multiplied. This also has an impact on the recycling of polyotefin waste which will also become more attractive as the range of applications for lhe recycled polyolefins increase and thus having a positive environmental impact.

A further advantage of this method is that some of the physical properties of the resultant performance enhanced polymeric material may exceed what would have been expected in a corresponding virgin poIyolefin . Thus although it would not previously have been considered practicable to combine such a low priced, low performance material as recycled polyolefin with a high priced, high performance material such as nanoclay. it has been found that due to the unexpected level of improvement in the physical properties of the recycled materia! ihat this combination is both cost and technically effective.

In one embodiment of the invention, prior to extruding the clay-polyolefin mix, the method further comprises:

adding a virgin polyolefin to one of the modified nanoclay. the recycled polyolefin or the day-polyolefin mix, and mixing.

in another embodiment of the invention, the method further comprises;

preparing a masterbaleh by mixing between 10% and 50% of the modified nanoclay by weight of lhe masterbatch with between 50% and 80% of a masterbatch polyolefin by weight of the masterbatch; end

mixing the masterbateh in the amount of between 5% and 40% by weight wilh a pαlyolefin matrix resin and extruding to provide the perfomiance enhanced polymeric material wherein

at least one of the masterbatch polyoϊefm or the polyolefin matrix resin is recycled polyolefin.

The advantage of preparing a masterbatch is that it results in better dispersability of the nanoday within the polyotefln.

In one embodiment of this invention, the masterbatch is directly extruded with the polyolefin matrix resin at a temperature of between 150°C and 260°C.

In another embodiment of this invention, the masterbatch is compounded with the polyolefin matrix resin to form a πanocomposile; and the nanocamposite is extruded at a temperature of between 150°C and 260°C,

In a further embodiment of the invention, the process further comprises;

preparing a masterbatch by mixing between 10% and 50% of the modified nanoclay by weight of the masterbatch wilh between 50% and 90% of a masterbatch polyofefin by weight of the masterbatch;

forming a polyolafin masterbatch by mixing between 10% and 50% of the masterbatch by weight of the polyolefin masterbateh with between 50% and 90% of a first pofyolefin matrix resin by weight of the polyotefϊn masterbatch;

mixing the polyolefin masterbatch in the amount of between 5% and

50% with a second polyolefin matrix resin and extajdϊng to provide the performance enhanced polymeric material; wherein

at least one of the masterbatch polyotefin, the first polyolefin matrix resin, or the second polyolefin matrix resin is recycled polyolefin.

It has been found that by providing two masterbatch steps, the dispersability of the nanoclay within the polyolefin is further increased,

In one embodiment of this invention, the poiyoiefin masterbatch is directly extruded with the second polyolefin matrix resin at a temperature of between 15O°C and 260°C.

In another embodiment of this invention, the polyolefin rnasterbaich is compounded with the second polyolefin matrix resin to form a nanocomposite, and the nanocomposite is extruded at a temperature of between 150°C and 260°C.

Preferably, the method further comprises grafting the masterbatch polyolefin with at least one monomer which is capable of reacting with the polyolefin in a molten condition. In one embodiment of the invention, the masterbatch polyolefin is grafted prior to adding the narøclay to the maslerbatch polyolefϊn. in another embodiment of the invention, the nanoclay is added Io the masterbatch polyolefin during grafting of the masterbatch polyolefin,

5 Preferably, the monomer is in the amount of lass than 2% by weight of the pofyolefin. Further preferably, the monomer is selected from the group comprising ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acids and anhydrides and mixtures thereof. Still further preferably, the monomer is maleic anhydride. 10

In one embodiment of the invention, the masterbatch pøiyoletϊn and polyolefin matrix resin are hornopolymers selected from the group consisting of one or more of polyethylene and polypropylene. Preferably, the polyethylene is selected from the group consisting of one or more of High Density Polyethylene (HDPE), Medium 15 Density Polyethylene (MOPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Law Density Low Molecular Weight Polyethylene (LDLMWPE).

In another embodiment of the invention, the masterbatch polyolefin and polyolefin matrix resins are copolymers selected from the group consisting of one or more of 20 bυtene-1 , hexene-1 , 4 methylpentene-1 (4 M P-I),

The invention also relates to a performance enhanced polymeric material prepared using recycled polyoiefin and by the method of the invention. The invention, further relates to a performance enhanced polymeric material comprising at least between 25 45% and 99% of a recycled polyoiefin and a modified nanoctay, and more preferably between 90% and 99% of a recycled polyoiefin.

Detailed Description of the Invention

30 The invention will be more clearly understood from the following description thereof:

All of the equipment used in carrying out each of the processes is well known equipment and accordingly does not require any further description. The performance enhanced polymeric material may be prepared by mixing modified nanoclay directly with recycled polyolefin and then extruding to provide the performance enhanced polymeric material.

It is also possible to mix the modified nanoclay with virgin polyolefin as well as recycled polydefin and extruding to provide lhe performance enhanced polymeric material.

In the above embodiments the amount of nanoclay added to provide ite performance enhanced polymeric material is between 1 % and 10% by weight of the material. The preferable amount of clay to be added to lhe recycled polyolefin or recycled and virgin polyolefin will depend on the amount and/or type of recycled polyolefin.

In the first embodiment of mixing nanoclay with recycled polyolefin only, the amount of clay required will depend on the grade and slate of the recycled polyolefin. Thus, more specifically, the lower the grade of the recycled polyolefin and the greater the damage to the recycled polyolefin, the higher proportion of day will be required,

In lhe second embodiment of mixing nanoclay with recycled and virgin poly olefin , the proportion of nanoclay required will depend on lhe grade and state of recycled polyolefin as well as tie amount of recycled polyolefin compared to virgtn polyolefϊn.

Generally, the most preferable amount of nanoclay is between 2% and 5% by weight of the performance enhanced material.

Alternatively a masterbatch can be prepared by mixing either recycled or virgin polyolefin or both with modified nanoclay. The masterbatch can be either combined by compounding with a polyotefin matrix resin to yield a nanocomposite material and then extruding or alternatively extrudfng the masterbatch and polyofefin matrix resin directly. It will be appreciated that if the masterbatch is prepared using modified nanoclay and virgin polyolefin only that at teast a portion of the polyolefin matrix resin will be recycled polyolefin.

The method of the invention may also comprise preparing a masterbatch by mixing either recycled or virgin polyolefin or both with modified nanoclay. The masterbatch may then be mixed with a first polyolefin matrix resin to form a polyolefin masterbatch. This pplyolefin masterbatch can then be mixed with a second polyolefin matrix to yield a nanocomposite material and then extruded or alternatively the pαlyotefin master batch and polyolefin matrix resin may be extruded directly. It will be appreciated that if the masterbatch is prepared using modified nanoclay and virgin polyolefϊn only that at least a portion of either the first or second polyolefin matrix restn will be recycled polyolefϊn.

In each of the embodiments, mixing of the nanoclay with polyolefin which is either recycled or virgin is generally carried out in an extruder. The mixing temperature can be between 150°C and 260°C and more preferably between 170°C and 230°C. Mixing can be carried out at speeds of between 30rpm and 100rpm for between 5 to 30 minutes.

In the specification the term "extrusion" refers to the compacting of material in a die. Extrusion may be in the form of extrusion blow moulding, rotomoulding, injection moulding or compression moulding. Blow moulding has been found to provide the most performance enhanced polymeric material. The clay-polyolefin mixes, masterbatches or nanocomposites which are extruded by blow moulding result in articles which have the most improved properties. During the blow moulding process the melted polyoleffn undergoes stretching in both the machine direction and transverse direction. This has the effect of orientating the polymeric chains of the polyotefin, This orientation ateo has the effect of orienting the clay platelets so that these platelets are aligned in a more parallel manner to each other. This parallel orientation results in increased physical properties such as improves flex modulus and resistance to permeation. Other process which give a degree of orientation such as fill blowing or pipe drawing can be usetf,

Either a single screw extruder or a twin screw extruder can be used for extrusion, however it will appreciated that the mixing capabilities of the twin screw extruder are considered to be more effective. It will further be appreciated that both single and twin screw extruders often have multiple heating zones. The extruder temperatures are in the region of between 150°C and 260°C, however the temperature of the individual zones of lhe extruder would vary waihin thfe range and increase gradually along the barrel of the extruder.

The performance enhanced polymeric material can either be extruded into a particular shaped article or can fas extruded or peflettsed for further processing such as moulding or further extrusion to a finished product.

The performance enhanced polymeric material can be made into a number of products including blovv-snoulded containers for transportation of dangerous goods such as chemicals, blow-moulded mussel floats, blow-moulded intermediate bulk containers, extruded pipes, blown film and other suitable types of polymeric products.

The addition of the nanoclays to the recycled polyolefins either dtreclly or in the form of a masterbatch transforms the recycled polyolefin from a low value polyolefin to a performance enhanced polymeric material The particular physical properties which have been shown to be enhanced include the modulus of stiffness, tensile strength, tensile modulus, and stress crack resistance.

The combination of nanoclay and recycled polyolefin results in a performance enhanced polymeric material with properties which far exceed the original properties of the recycled polyolefϊn and even the properties of a corresponding virgin polyolefin.

Due to the condition of recycled polyolefin following use and recycling, it would not previously have been considered possible to return the recycled polyolefin even to its original condition. Specifically due to the level of polymeric chain scission it would not have been considered possible to add any type of component to the recycled polyolefin which would result in reformation of the polymeric chains.

It has been found that even though the nanoclays do not cause the polymeric chains to reform, that they result in a technical effect which exceeds what would have been expected if the polymeric chains did reform_*

The nanoclay which is added may be a natural or synthetic sitieate day. Suitable types of nanoclays are the smectite clays which include montmorillonite, saponite, beidellite. nontronite and hectorite or any analogue thereof. The nanoclay should also be modified by a cation exchange with an alky! ammonium son as this allows a better interaction wilh the polyolefϊns. The nanoclay has a large surface area for interaction wilh the polyolefin and comprises swellable nanoclay platelets which disperse within 5 the polymeric chains of the recycled polyolefin. It has been found that the nanoclay platelets both assist in increasing the formation of crystalline sites on ihe polymeric chains and in plating out the amorphous regions of the chains. It has also been found that the nanoclay platelets fill the gaps in the polymeric chains which have been caused by chain scission. This results in a polymeric material with increased 10 strength and enhanced physical properties.

All types of recycled polyolefin are suitable for this invention. Recycling can involve either or both of mechanical or chemical recycling, but more commonly only mechanical recycling is carried out. Mechanical recycling of polyolefins Involves 15 sorting of the plastic items into their specific polyolefin types. This is generally carried out by x-ray fluorescence or flotation methods. The plastic items are then washed and any labels are removed. Each item is then sliced into flakes, rewashed, melted together, and extruded through small holes to form small plastic pellets.

20 The molecular weight of the virgin pαiyolβfϊn will depend on the type of potyαlefin used, however generally wall be in the region of between 200,000 and 700,000 daltαns. The virgin polyolefins will generally have a melt index of 2-3g/10 mfn at 21 ,6 kg soad and 190°C, and a viscosity of between 1500 Pas and 1700 Pas at a shear rate of 100 1/s,

25 Other optional components which are typically used in polymeric material processing such as pigments can be added.

The following examples are given by way of illustration only and should not be construed as limited the subject matter of the invention. 30

Examples

In each of ihe examples the following materials were used: Recycled polyolefin:

Recycled polyethylene: The recycled polyethylene was a high molecular weight polyethylene in the form of a 200L drum. The drum was originally made using HM5420 supplied by BP Chemicals Ltd in 1999, The original use of the drum is unknown, however prior to this experiment it is known that the drum had been used as a marine float. The drum was first washed wilh water to remove all contamination and chipped into pellets circa 1-5 mm.

Recycled polypropylene: The recycled polypropylene was obtained from chipping up transport pallets. The age and grade of the polypropylene was unknown.

Nanoclay: The nanoclay used was Nanomer I30P sourced from Nanocor Inc., which had been organically modified by cation exchange vvilh an alkyl ammonium ion,

Virgin polyolefin:

The virgin polyolefin used was a virgin polyethylene from orte of the following sources:

A) Commercially available mateafed High Density Polyethylene (HOPE), Fusbond MB100D which was sourced from DυPont.

B) Commercially available High Density Polyethylene (HDPE), Fina SI508

C) Commercialϊy available High Density Polyethylene (HDPE), Lupoten

D) Commercially available Low Density Polyethylene (LDPE), Esααn 6101 Example 1; Mechanical properties of recycled polypropylane plus nnnoclay prepared on a Brabonder Plastograph EC.

Test Material A

38g of recycled polypropylene and 2g of modified nanoclay were added to a Brabender plastograph EC at 210°C. The polypropylene and nanoclay were then mixed for 10 minutes at 60rpm to form a day-polyolefin mix. The resulting mix which contained 5% nanoclay was then compression moulded and tested according to ISO 178 to determine the flex modulus.

The flax modulus of a sample of recycled polypropylene with no clay was also tested for comparison purposes. The flex modulus results are shown in Table 1.1.

Table 1.1

Example 2: Mechanical properties of recycled polyethylene and virgin polyethylene compared to performance enhanced polymeric material prepared from recycled polyethylene.

Test Material S

THe preparation of a performance enhanced polymeric material υsing a recyci&d high molecular weight poSyeihylene ^vas carrfed out υsing the following method and according to the quantities ouliined in Table 2, 1. Table 2.1

The na nods y and master batch polyolefin were first compounded in a Dr Collin ZK25 twin screw extruder to yield a masterbatch. The extruder parameters are outlined in Table 2.2,

Table 2.2

The masterbatch was then extruded with polyolefin matrix resin in a Killion 38mm single screw extruder to provide extruded sheets of performance enhanced polymeric material. The extruder parameters are outlined in Table 2.3,

Table 2.3

Test Material C

The preparation of a performance enhanced polymeric material using recycled high molecular weight polyelhyfene was carried out by directly extruding the nanoclay, virgin polyethylene and recycled polyethylene in a Dr CoIBn ZK25 twin screw extruder according to the quantities outlined in Table 2.4.

Table 2,4

The extruder parameters are outlined in Table 2.5.

Table 2,5

Further extrusion was then carried out in a Killion 38mm single screw extruder to provide extruded sheets of performance enhanced polymeric material The processing parameters of the singte screw extruder were the same as for Test Material B (Table 2,3), with the exception thai the lower line speed of the extruder was 0.195 m/min.

Test Material D

The recycled polyethylene was fed directly into ths Killion 38mm single screw extruder to provide an extruded sheet as a reference sample. The processing parameters of the single screw extruder are the same as for Test material B (Table 2.3}, with the exception of (he following parameters outlined in Table 2.6

Table 2.6

Physical testing

Flexural modulus was evaluated on the resultant 2 mm sheets using 60mm long, 12mm wide strips, a test span of 40mm and a test speed of 2mm/min. In all other 10 respects the testing complied to ISO178.

The properties of the test pieces are shown in Table 2.7.

Table 2.7: Mechanical Properties of test pieces and standard.

Table 2.7 shows increased Flex Modulus for clay containing recycle compared to the reference recycle material only. Typical flex modulus results for the original virgin polyethylene from which the drum was made is circa 1 100 MPa showing that clay has raised the stiffness of the recycle to in excess of lhe original material.

Example 3: Mechanical Properties of recycled polyethylene plus nanoclay prepared on Brabender Plastograph EC.

A masterbatch of modified nanoday and virgin polyethylene was prepared by grinding both materials to powder, dry blending and then feeding them into a Dr Collin ZK25 twin screw extruder and extruding as pallets.

The extruder parameters are outlined in Table 3.1.

Table 3.1

The masterbatch was then added to recycled polyethylene in a Brabender

Plastograph EC according to the quantities outlined in Table 3,2,

Table 3,2

The masterbatch and recycled polyethylene were mixed over a 2 minute period followed by a further 8 minutes mixing at 185°C at 60rpm. The resulting mixture was then transferred and extruded by compression moulding to give 3mm plaques. The test materia! plaques were tested for flexural modulus according to ISO 178.

The flex modulus results are shown in Table 3.3.

Table 3.3

Example 4: Mechanical properties of recycled potyethyϊene plus nanoclay prepared in a twin screw extruder and then blow moulded to give 10 litre containers

Test material I

40% nanoclay, 30% virgin HDPE, and 30% virgin LDPE were mixed in a Berstoff BD15 40mm twin screw extruder to form a masterbatch comprising 40% nanoday. 68% of this masterbatch was mixed with 32% Fina SI508 virgin HDPE in the same twin screw extruder to farm a polyoSefin masterbatch comprising 27.2% nanoday. This polyolefin rnasterbatch was then mixed in a Bekum 10 litre blow moulder, 18% of this polyolefin masterbatch was than mixed with recycled polyethylene to yield a performance enhanced materia! comprising 4.8% nanoclay.

Test Material J 4,7% nanoday was added direclly to 93% recycled polyethylene and 2% blue pigment and extruded in a Bekum 10 litre blow moulder.

Test Material K

40% nanoclay and 60% virgin polyethylene were mixed to form a maslerbatch comprising 40% nanoclay. 25% masterbatch was mixed with virgin Lupolen HOPE in the Berstoff BD15 40mm twin screw extruder to form a polyolefin maslerbatch comprising 10% naπocfay. 50% of this polyofefln masterbatch was then mixed with

50% recycled polyethylene in a Bekum 10 litre blow moulder to yield a performance enhanced material comprising 5% nanoclay.

Two tests were performed on the test materials. The first of these tests was a stack test and was carried out according to that used In ISO 16104. The loading on the container was 2.5SG which in this case (10 litre containers) was 300kg. the temperature was held at 40°C and the containers were filled with wetting agent. The number of days was recorded until the containers failed the stack test. All tests were repeated and an average was taken.

The second test performed was the visual examination of the containers where we examined for evidence of poor dispersion.

The results of both tests are tabulated in Table 4.1

Table 4.1

The above results show a more that doubling in stack test performance although ihe visual appearance suggests that test material K is the optimum.

In this specification the terms "comprise, comprises, comprised and comprising" and the terms include, includes, included: and including" are all deemed totally interchangeable and should be afforded the widest possible interpretation,

The invention is not limited to the embodiments hereinbefore described which may be varied in both construction and detail within trie scope of (he claims.

Claims

1. A method of transforming a recycled polyolefin into a performance enhanced polymeric material;

characterised in that:

The method comprises mixing a modified nanoclay with the recycled polyolefin to form a clay-polyolefin mix; and

extruding the clay-polyofefin mix to form the performance enhanced polymeric material.

2. A method of transforming a recycled poϊyolefϊn as claimed in claim 1, wherein prior to extruding the clay-polyolefin mix, the method further comprises:

adding a virgin poiyoleftn to one of the modified nanoclay, the recycled polyolefin or the clay-polyolefin mix, and mixing.

3. A method of transforming a recycled polyolefin as claimed in claims 1 or 2, further comprising:

preparing a mastertiatch by mixing between 10% and 50% of the modified nanoclay by weight of the masterbatch with between 50% and

90% of a masterbatch polyolefin by weight of the masterbatch; and

mixing the masterbatch in the amount of between 5% and 40% by weight with a polyolefin matrix resin and extruding to provide the performance enhanced polymeric material; wherein

at least one of the maslerbateh pαlydefin or the polyoSefin matrix resin is recycled poiyofefin.

4. A method of transforming a recycled polyolefin as claimed in claim 3, wherein the masterbatch is directly extruded with the polyolefin matrix resin at a temperature of between 150°C and 260°C.

5

5. A method of transforming a recycled polyolefin as claimed in claim 3, wherein the masterbatch is compounded with the polyofefin matrix rosin to form a nanocomposite; and

10 the nanocomposite is extruded at a temperature of between 1 SCTC and

260°C.

6. A method of transforming! a recycled polyolefin as claimed in claims 1 or 2, further comprising: 15 preparing a masterbatch by mixing between 10% and 50% of ihe modified nanoclay by weight of the masterbatch with between 50% and

90% of a masterbatch polyolefin by weigh! of the masterbatch:

20 Forming a polyotefϊn masterbatch by mixing between 10% and 50% of the masterbatch by weight of the poiyσlettn masterbatch with between 50% and 90% of a first polyolefin matrix resin by weight of the polyofefin masterbatch;

25 mixing the polyolefin masterbatch in the amount of between 5% and

50% with a second polyolefin matrix resin and extruding to provide the performance enhanced polymeric material; wherein

at least one of the masterbatch polyotefK the first polyolefin matrix 30 resin, or the second polyolefin matrix resin is recycled polyolefin.

7. A method of transforming a recycled polyotøfin as claimed in claim 6, wherein the poiyoϊafin masterbatch is directly extruded with the second polyoieftn matrix resin at a temperature of between 150⁸C and 260*C.

8. A method of transforming a recyded polyolefin as claimed in claim 6, wherein the polyolefin masterbatch is compounded with the second polyolefin matrix resin to form a na nocomposits; and

5 the nanocomposite is extruded at a temperature of between 150°C and 260°C,

9. A method of transforming a recycled polyolefin as claimed in any of claims 3 to 10 8, further comprising:

grafting the masterbatch polyolefin with at least one monomer which is capable of reacting with the polyolefin in a molten condition,

15 10. A method of transforming a recycled polyolefin as claimed in claim 9, wherein the masterbatch polyolefin is grafted prior to adding the nanoclay to the masterbatch polyolefin.

11. A method of transforming a recycled polyolefin as claimed in claim 9, wherein 20 the nanoclay is added to the masterbatch polyolefin during grafting of the masterbatch polyolefin,

12. A method of transforming a recycled polyolefin as claimed in any of claims 9 to

11, wherein the monomer is in the amount of tess than 2% by weight of the 25 polyolefin.

13. A method of transforming a recycled polyolefin as claimed sn any of claims 9 to 12, wherein the monomer is selected from the group comprising ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic adds and 30 anhydrides and mixtures thereof,

14. A method of transforming a recycled polyotefin as claimed in any of claims 9 to 13, wherein the monomer is male to anhydride.

15. A method of transforming a recycled polyolefin as claimed in any of claims 3 to 14, wherein the masterbatch polyofefin and polyotefin matrix resin are homopolymers selected from the group consisting of one or more of polyethylene and polypropylene.

5

16. A method of transforming a recycled polyolefin as claimed in claim 15, wherein the polyethylene is selected from the group consisting of one or more of High

Density Polyethylene {HOPE), Medium Density Polyethylene (MOPE), Low

Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Low 10 Density Low Molecular Weight Polyethylene (LDLMWPE)..

17. A method of transforming a recycled potyolefin as claimed in any of claims 3 to 14, wherein the masterbatch polyolefin and polyolefin matrix resins are copolymers selected from the group consisting of one or more of butene-1, hexene-1 , 4 methylρentene-1 (4 MP-1 )

18. A performance enhanced polymeric material prepared using recycled polyolefin and by the melhod as claimed in any preceding claim.

19. A performance enhanced polymeric material comprisfng at teast between 45% and 99% of a recycled pølyolefiri and a modiπed nanoclay.