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The Development of a Maleic Anhydride Grafted Polyethylene for use

as a Compatibiliser with High Density Polyethylene and Nanoclays


Michael Gunning, Cormac Byrne, Paul Blackie
Centre for Nanotechnology and Materials Research, Athlone Institute of
Technology, Dublin Rd. Athlone, Co. Westmeath, Ireland

Abstract
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

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.

Fig 3: How Fusabond works Fig 4: Intercalation of Clay


Fusabond provides a link between the polymer material and Intercalation is the process wherein the clay
other materials such as metals and minerals. The polymer gallery spacing has increased, due to the
chain of fusabond is miscible with the primary polymer and process of surface modification. Under the
Fig 2 shows the structure of Maleic Anhydride the grafted maleic anhydride group interacts with the proper conditions of temperature and shear, an
grafted polyethylene additive. This acts as a compatabiliser for the two materials intercalate is capable of exfoliating in a resin
and makes an otherwise impossible blend possible. [3] matrix. The most common of these being melt
processing. [4]
Results & Discussion

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
Fig 5: FTIR Spectra comparison of Fusabond and
flexular modulus and flexular strength. Despite the fact that run
various blends made with Benzoyl Peroxide (BP) as 15 contains less grafted Maleic Anhydride it has worked better
the initiator than Fusabond, this may be due to it’s rheological properties as
Grafted Maleic Anhydride is represented by the shown in Fig 10
peak at 1790cm-1 which is evident in the spectra
Fig 10: Rheological data for Run 15, Fusabond and
for fusabond. This peak is not evident in any of 51090 HDPE
the blends made with BP.

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
Fig 8: Flexular Modulus data for blends containing 3wt% an unsuitable initiator. The use of DiCumyl
Fig 6: FTIR spectra for Run 15 and Fusabond of Runs 1-21, Fusabond and virgin HDPE 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.
Fig 7: % Maleic anhydride grafted for runs 1-21 made Moad Polymer Science 1999; 24; 81-142 )
Fig 9: Flexular Strength data for blends containing 3wt% 3 www. Dupont..com
with dicumyl peroxide as the initiator and Fusabond of Runs 1-21, Fusabond and virgin HDPE 4 Nanocomposite science and technology (Pulickel M. Ajayan)

Acknowledgements Corresponding author: Mgunning@ait.ie

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