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TheThe DevelopmentDevelopment ofof aa MaleicMaleic AnhydrideAnhydride GraftedGrafted PolyethylenePolyethylene forfor
TheThe DevelopmentDevelopment ofof aa MaleicMaleic AnhydrideAnhydride GraftedGrafted PolyethylenePolyethylene forfor

TheThe DevelopmentDevelopment ofof aa MaleicMaleic AnhydrideAnhydride GraftedGrafted PolyethylenePolyethylene forfor useuse asas aa CompatibiliserCompatibiliser withwith HighHigh DensityDensity PolyethylenePolyethylene andand NanoclaysNanoclays

Michael Gunning, Cormac Byrne, Paul Blackie

Centre for Nanotechnology and Materials Research, Athlone Institute of Technology, Dublin Rd. Athlone, Co. Westmeath, Ireland

AbstractAbstract

Research and development of nanofilled polymers has greatly increased in recent years. Research into the use of carbon nanotubes in the early 90’s prompted

investigation into other nanoparticles. These nanofillers come in the form of platelets of a thickness as small as a couple of nanometers. They will usually stack on

top

of each other to form tactoids and these tactoids can contain up to hundreds of layers of platelets. Because of the high polarity of these nanoclays they do not

mix

readily with polymers, as such a compatibiliser is needed to provide a link between polymer and nanoclay [1] . Maleic Anyhdride is one commonly use grafting

agent for this task [2] . Grafting is a process in which monomers are covalently bonded onto the polymer chain. Considerable work has been done in recent years on

the different techniques of grafting. These techniques include chemical, radiation and reactive extrusion. Of these processes this study is concerned with radical

induced grafting by reactive extrusion. Fusabond is the commercially available Maleic Anhydride grafted polyethylene and this project aims to replace this.

Methodology

and this project aims to replace this. Methodology FIG 1: (A) (B) (C) (D) Fig1(A) Shows

FIG 1: (A)

(B)

(C)

(D)

Fig1(A) Shows the structure of HDPE ,the functionalisation of HDPE was achieved by reactive extrusion. This involved the use of an initiator, either Benzoyl Peroxide (B) or DiCumyl Peroxide

(C) in order to create radical sites on the HDPE

backbone where the monomer Maleic Anhydride

(D) can graft.

backbone where the monomer Maleic Anhydride (D) can graft. Fig 2 shows the structure of Maleic

Fig 2 shows the structure of Maleic Anhydride grafted polyethylene

shows the structure of Maleic Anhydride grafted polyethylene Fig 3: How Fusabond works Fusabond provides a

Fig 3: How Fusabond works

Fusabond provides a link between the polymer material and other materials such as metals and minerals. The polymer chain of fusabond is miscible with the primary polymer and the grafted maleic anhydride group interacts with the additive. This acts as a compatabiliser for the two materials and makes an otherwise impossible blend possible. [3]

Results & Discussion

impossible blend possible. [ 3 ] Results & Discussion Fig 4: Intercalation of Clay Intercalation is

Fig 4: Intercalation of Clay

Intercalation is the process wherein the clay gallery spacing has increased, due to the process of surface modification. Under the proper conditions of temperature and shear, an intercalate is capable of exfoliating in a resin matrix. The most common of these being melt processing. [4]

The most common of these being melt processing. [ 4 ] Fig 5: FTIR Spectra comparison

Fig 5: FTIR Spectra comparison of Fusabond and various blends made with Benzoyl Peroxide (BP) as the initiator

Grafted Maleic Anhydride is represented by the peak at 1790cm-1 which is evident in the spectra for fusabond. This peak is not evident in any of the blends made with BP.

This peak is not evident in any of the blends made with BP. Fig 6: FTIR

Fig 6: FTIR spectra for Run 15 and Fusabond

made with BP. Fig 6: FTIR spectra for Run 15 and Fusabond Fig 7: % Maleic

Fig 7: % Maleic anhydride grafted for runs 1-21 made with dicumyl peroxide as the initiator and Fusabond

Prominent peaks at 1790cm-1 can be clearly seen in Fig 6 indicating that succesful grafting has occurred. From these peak heights the % Maleic Anhydride which is grafted to the polymer chain is worked out. This is shown in Fig 7. Fig 8 & 9 show the flexular modulus and flexular strength data for blends made up using 3wt% of these grafted materials. It can be seen that Run 15 outperforms Fusabond for both flexular modulus and flexular strength. Despite the fact that run 15 contains less grafted Maleic Anhydride it has worked better than Fusabond, this may be due to it’s rheological properties as shown in Fig 10

be due to it’s rheological properties as shown in Fig 10 Fig 8: Flexular Modulus data

Fig 8: Flexular Modulus data for blends containing 3wt% of Runs 1-21, Fusabond and virgin HDPE

containing 3wt% of Runs 1-21, Fusabond and virgin HDPE Fig 9: Flexular Strength data for blends

Fig 9: Flexular Strength data for blends containing 3wt% of Runs 1-21, Fusabond and virgin HDPE

containing 3wt% of Runs 1-21, Fusabond and virgin HDPE Fig 10: Rheological data for Run 15,

Fig 10: Rheological data for Run 15, Fusabond and 51090 HDPE

Conclusions

From the results obtained it may be seen that grafting of Maleic Anhydride onto the polyethylene backbone is possible. It is dependant on a number of factors and it has been shown in this work that benzoyl peroxide is an unsuitable initiator. The use of DiCumyl Peroxide produced good grafting yields. Furthermore the improvement in properties of nanocomposites is not solely dependant on the % Maleic Anhydride present in the compatibiliser, rheology can affect how miscible the polymer, compatibilser and additive are.

References

1 Fracture toughness of high density polyrthylene-g-MA/montmorillonite nanocomposites (S.C. Tjong, S.P. Bao, Composites Science and Technology; 67;2007;314-323)

2 The synthesis of Polyolefin graft co polymers by reactive extrusion (G. Moad Polymer Science 1999; 24; 81-142 )

3

4 Nanocomposite science and technology (Pulickel M. Ajayan)

www. Dupont

com

Acknowledgements

Corresponding author: Mgunning@ait.ie

com Acknowledgements Corresponding author: Mgunning@ait.ie Create PDF files without this message by purchasing

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