Maleation of Polyoleftn alld its Application: A Brief Guide and Review (Sunit Hendrana)

MALEATION OF POLYOLEFIN AND ITS APPLICATION:A BRIEF GUIDE AND REVIEW

Sunit Hendrana

Research Centre/or Physics (P2F) - LfPfJI. Cisitu 211J54D, Sangkuriang, KomplekLfPI. Bandung

ABSTRACT

MALEATION OFPOLYOLEFIN AND ITS APPLICATION : A BRIEF GUIDE AND REVIEW. Maleation of

polyolefin plays important roles development of new material based on polyolefin. Polyolefin-based nanomaterialalso widely applies maleated polyolefin. Therefore, understanding of the process and technology is very important.This paper discusses the current developments and understanding of maleation of polyolefin. A brief descriptionon the mechanism, including factors affected the process, problems encountered and its solutions and applicationsof the materials produce will be presented.

Key words: Maleation, polyolefin, nanomaterials

ABSTRAK

MELEASI POLiOLEFIN DAN APLIKASINYA: PETUNJUKSINGKATDANTlNJAUAN. Maleasipoliolefinmempunyai peranan yang sangat penting dalam pembuatan material baru. Nanomaterial yang menggunakan berbasispada polyolefin tennaleasi. Oengan demikian, pemahamam proses dan teknologi maleasi polio Ie fin menjadi sangatpenting. Oi dalam paper ini akan menguraikan secara siI1Ekatmekanisme, faktor-faktor yang mempengaruhi, kendala

dalam proses dan pemecahannya untuk menghasilkaJ1 maleasi polioelfin yang diinginkan.

Kata kunci : Maleasi, poliolefin, nanomateria/s

INTRODUCTION

Research on the maleation of polyolefin

in Indonesia has paid a lot of attention. Maleationof polyolefin itself has been applied for longtime [1,2]. In the development of new materials

functionalized polyolefin plays important rolebecause the functionality ofthe materials itself.

Maleation of polyolefin can be used as a bridgebetween starch and polyolefin in producingbiodegradable polymer [3,4], for adhesion

agent or compatibilization agent in polymer blend[5-8], and recently is applied in polymernanocomposites [9].

The Maleation can be carried out by using

solvent [7,8] as a medium or by using reactive

extrusion [10-18] where the melting polymer is. reacted with unsaturated monomer. The monomer

commonly used is maleic anhydride (MAH). Some

aspect of the Maleation such as the effect of thepolyolefm structure, and the challenge to improve

of the grafting will be discussed.

THEORY

Monomers and Macromonomers

There are many monomers andmacromonomers available for functionalization of

polyolefin. Type of monomers (structure 1-4) areillustrated in the Figure 1. below [19].

~

~oo~o0=1:>=0x o 0

" / ,0

RR

\ R(1)

(2} (3)(4)

Figure 1. Types of monomers commonly usedin functionalization of poly olefin.

Macromonomers can also be applied .

Requirement for macromonomers used as graftingagent is the present of reactive double bond whichenable for free radical addition. The advantages

of using macromonomers is its low-ability for

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Prosiding Simposium Nasional Polimer V

homopolymerization, however it suffer fromresidual W1reacted macromonomer which is more

difficult to remove by simple method, i.e, vacuumheating. In other words, monomers or

macromonomers having no or less ability toproduce homopolymer and high volatilemonomers or macromonomers are the most

preferable ones. Other factors have to be

considered in applying a monomer or

macromonomer for fimctionalization purpose. Thefactors are [16] the monomers concentration,

solubility of the monomers in the reaction system,method of introducing monomer to the reaction

system, and the reactivity of the monomer withinitiator radicals as well as with substrate derivedradicals.

MAH is the common monomer used for

fimctionalization of polyolefin. One of the reasonsthat the monomer does not produce polymer

durin~opolymeri;tion (or functionalization)proce~hus~singte..m6nomer grafting can beachieved. Besides that, residual MAH can be

removed by simple method. Non-published data

yet produce in our laboratorium shows thatresidual MAH can be removed by vacuum oven.

Factor Affecting Radical Reaction

Some factors have to be considered in

order to optimize reaction. There are temperature,

pressure and viscosity. Usually higher temperaturelowering radical reaction. Other factor regarding

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with temperature may involve such as the ceiling

temperature of the monomers. The ceilingtemperature increase over higher pressure andmonomer concentration.

Pressure of the reaction (usually in the meltprocessing) affect on bond scission. While

viscosity of the media will influence the diffusion

controlled process. Higher viscosity of media may

reduce initiator decomposition rate and efficiency.

Effect of the Polymer Structure

Recent results show that the polyolefin

structure will affect on the copolymerization(grafting) itself. Machado's works show that the

degree of grafting affected by the propene contentof the polyolefin [20]. The degradation duringprocess also affected by the propene content [20].

The other polymer structure's factor which

could influence the grafting reaction are [12]:(i) the amount of tertiary hydrocarbon per chain

length, (ii) the presence of antioxidant and otherstabilizers, (iii) the branch, short chain branch oralpha-olefin comonomers, and (iv) molecular

weight of polyolefin itself.

Maleation of Poly olefin

It is commonly known that maleation on

polyolefin produce different effect. Maleation ofpolyethylene (PE) produce x-link of the polymers.

While maleation of polypropylene (PP) undergoesdegradation because of the chain scission.

(5)

(8)

(11)

(6)

(9)

(T)

~o

(10)

(12)

Figure 2. Different structure ofmaleated PP (as cited fromreference 19).

292

Maleation of Polyolefin and its Application: A Brief Guide and Review (Sunil Hendrana)

Cha.in ..• nd

BKkbon~

o~T p~

~

o (10)

~~(15)

0

Figure 3. Different structure ofmaleated PE (as cited from reference 21)

Maleation on PP also produces differentstructure to maleated PE. The structure (5-12) ofmaleated PP can be shown in Figure 2 (as citedfrom reference 19).

The different structure of maleated ofPE

can be shown in Figure 3 (structure 13-16).

Recent Understanding and Developments

The clarity of maleated usually notmeet expectation. Yellowness of the product if theorigin of the problem. The recent works showsthat the yellowness caused by the present of theolygomer of the maleat (MAH). (Note: theprevious understanding says that MAH will notundergomonomeradditionto monomerwmch willproduce homopolymer). This constrain alreadysolve by designing reaction with reactive

e?'trusion [22].Using high resolution NMR, YANG,et.el.,

investigates the structure of PE-g-MAH. The

R·H

Hydrogena_on

results show some different structures

producing from the reaction of PE-g-MAHmacroradicals. The structures are as mention

in Figure 4.A new improvement also been achieved in

development ofinitiator to reduce degradation ofpolymer during process. Borone/02 radicalinitiator is used to graft MAH onto PP with nodegradation [24].

CONCLUSION

Functionaliztion of Polyolefin is veryimportant materials for developing new materials

- and nanomaterials. Some development has beenachievedin understanding of the process, structureand characterization as well as initiator. The

development could be used to design of thefunctionalization to produce desiredfunctionalized-polyolefinstructure.

+

o

Strudure I StnKture II

~o-J-A:jO° 0

SlnJdure 11

Structure III

Figure 4. The reaction continuation based on PE-g-MAH as observed by Highresolution NMR [23]

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Prosiding Simposium Nasional Polimer V

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