B19MA1

Step-growth polymerisations

Step-growth vs. chain-growth polymerisation

Step-growth polymerisations are characterised by the stepwise reaction between the reactive groups of bifunctional monomers. Each step re uires an activation energy to be overcome and high temperatures are often essential throughout the course of the polymerisation. !uring a step-growth polymerisation process" any two species can react" for e#ample two monomers" a monomer and a dimer" two dimers" an oligomer and a dimer" and so on. Although monomers are consumed rapidly during the reaction" the molecular weight and with it the degree of polymerisation of the products increase very slowly. $his contrasts with chain-growth polymerisations where high-molecular-weight polymer is produced within a few seconds" and only the yield increases gradually over time. Condensation polymers are prepared from condensation reactions such as those between a diacid %or diester& and a dialcohol to produce a polyester. 'or e#ample" the transesterification of ethylene glycol %a diol& and dimethyl terephthalate %a diester& yields poly%ethylene terephthalate&" a polyester( ) +,*) ) )*+, +) *+*+)+ -./ 0* *alcium acetate %catalyst& ) ) ) ) *+- *+n %-n-1& *+,)+ A characteristic feature of a condensation polymerisation is the elimination of a small molecule %water" +*l or in the case above methanol&. +ence" the chemical composition of the repeat unit differs from that of the reacting monomers. $he formation of polyurethanes from the reaction of diols and diisocyanates or the ring-opening polymerisation of cyclic monomers such as -caprolactone or -caprolactam does not involve elimination of a small molecule. 1evertheless" the 2inetics of polymer formation are typical for step-growth polymers which re uire time to build up the polymer chain. ) -*aprolactam 1+

!imethyl terephthalate

Ethylene glycol

cat. +-) or 1a)*+, or +*l

) *+-*+-*+-*+-*+1 + 3oly%-caprolactam& n

Carothers' equation
$he degree of polymerisation" xn" e uals No4N and is a simple function of conversion" p %/ p 5 1&" and is e#pressed mathematically by *arothers6 e uation.

xn =

1 1 p

%Carothers' equation&

t h g i w r a u c e l o M
/

7 *onversion

1//

$o achieve high degrees of polymerisation" conversion must be very high %997&" monomers must be pure %i.e. monofunctional impurities should be absent&" and the stoichiometry must be precisely e uimolar.

An imbalance in stoichiometry between the monomers used will reduce the degree of polymerisation8 this is 1+r ta2en into account in the modified *arothers6 e uation( xn = . 9n practice" this means that a 17 1 + r 2rp imbalance in the stoichiometry of the functional end groups % i.e. r : /.99& leads to a considerable drop in the

B19MA1

Step-growth polymerisations
1 + 0.99 = 199 even at a theoretical 1//7 1 + 0.99 2 0.99

ma#imum possible degree of polymerisation xn =

conversion. Such addition of a monofunctional impurity %acetic acid& is used in the industrial production of nylon-;"; to limit the degree of polymerisation to about 1//.

At a first appro#imation" the number-average chain length increases linearly with time confirming that stepgrowth polymerisations re uire time to produce high-molecular-weight polymer( x n 1 + A 0 kt

[ ]

Gel formation
9f a step-growth polymerisation contains some monomer with a functionality < -" and if the reaction is carried out to high enough conversion" a crosslin2ed polymer or gel may be formed. A gel is defined as a polymer of essentially infinite molecular weight" e#tending throughout the reaction mass. =els don6t dissolve any more in any solvent" but are easily swollen by a good >solvent> or li uid monomer. A A A A A A A

Multifunctional monomers are often used in the production of thermosetting polymers % e.g. epo#y resins" melamineformaldehyde resins" ba2elite&.

Typical step-growth polymers

?nderneath are the structures of repeat units of important polymers you can ma2e by step-growth polymerisation. Name or Class Nylon 6 3oly%-caprolactam& Nylon 6,6 3oly%he#amethylene adipamide& Poly(ethylene oxide) ) Poly(ethylene terephthalate) ) *+, Polycarbonates * *+, *+, Polysiloxanes Si ) *+, Polyurethanes n 3rinting rollers" sealing and Dointing Repeat Unit ) 1+ *+* @ 1+ *+) 1+ * ; Uses !rip-dry fabrics" cordage" braiding" bristles" and %nonbiodegradable& surgical sutures ) * A n Because of its water-solubility used in eye drops" ointments" la#atives 'abrics" plastic bottles" tyre-cord yarns" and yacht sails n ) ) * ) n *!s" !B!s" cooling fans" marine propellors" safety helmets As above

*+-

) *+- *+n ) ) *+- *+-

=as2ets" door seals" fle#ible moulds for medical applications

) ) C1 1+ * ) C- ) * 1+

'or more bac2ground on 3olymer *hemistry" see the Birtual 3olymer Eab on Bision.

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