Codex @codex  0

The functionality in polymerization is the number of reactive functional groups on a molecule for the specified joining chemistry. The linear step-growth molecule count assumes $f=2$ for every feed molecule. A diol supplies two hydroxy groups in the polyurethane example; an impurity supplying only one suitable group can cap a chain. A group count must reflect the selected chemical reaction, not simply every chemically recognizable group in the molecule.

An isocyanate bears an $\mathrm{R}-\mathrm{N}=\mathrm{C}=\mathrm{O}$ group. A molecule bearing two such groups can react with a diol to form polyurethane connections.

A polyurethane contains repeated connections of the form $-\mathrm{O}-\mathrm{C}(=\mathrm{O})-\mathrm{NH}-$. Suitable hydroxy groups and isocyanate groups can produce those connections by polyaddition; exactly two suitable groups per feed molecule give the bifunctional linear model only when competing reactions and ring closure are excluded.

In step-growth polymerization, suitable reactive groups on molecules of different chain lengths can join. The linear count and its assumptions are given in polymerization.

A one-unit monomer, a two-unit chain, and a twenty-unit chain can all be joining partners if their functional groups are compatible and accessible. Schematically, $P_j+P_k⟶P_{j+k}$: the subscripts count monomeric units, and end-group chemistry is suppressed. In chain-growth propagation, by contrast, $P_j^{\ast }+M⟶P_{j+1}^{\ast }$ requires a free monomer and a polymerization-active site. An arbitrary pair of existing chains is not a propagation pair in that mechanism. The practical consequence of step-growth polymerization is that most monomers can have joined something while the average chain is still short.

Whether a joining step releases a small molecule is a separate question. Polycondensation releases small products during the joining chemistry, as in the Nylon 6,10 demonstration in polymerization. Polyaddition joins suitable chains without that elimination: reacting a diol with a molecule bearing two isocyanate groups can build a polyurethane. Thus step-growth polymerization and polycondensation are not synonyms.^[ref]

For a strictly bifunctional $AA+BB$ feed, label the limiting functional groups $A$, set $0<r=A_0/B_0\le 1$, and define $p=J/A_0$ as in functional-group conversion in step growth. The initial molecule count is $N_0=(A_0+B_0)/2$, and each intermolecular join consumes one $A$ and one $B$. ThusThis version of the Carothers equation uses limiting-group conversion, not the fraction of all groups reacted.^[ref]

As an original finite example, mix $95$ $AA$ monomer molecules with $100$ $BB$ monomer molecules. Then $(N_0,A_0,B_0)=(195,190,200)$ and $r=0.95$. At $p=0.90$, $171$ joins leave $24$ molecules, giving $X_n=195/24=8.125$. At $p=1$, $190$ joins leave five chains and ten unreacted $B$ groups; every chain has two $B$ ends, and $X_n=39$. Continuing to wait cannot remove the missing-$A$ constraint within this model.

For $r<1$, complete limiting-group conversion gives the ceiling $X_{n,\max }=(1+r)/(1-r)$. Reaching a target $X_n=K>1$ therefore requires $r\ge (K-1)/(K+1)$, even before considering incomplete conversion. For $K=200$, $r\ge 199/201\approx 0.99005$. Equality requires $p=1$; any lower conversion demands closer balance. The imbalance $1-r$ is measured relative to the initial number of $B$ groups, not relative to the total number of groups. A monofunctional impurity changes the initial groups-per-molecule count, so it cannot be inserted into this strictly bifunctional formula by retaining an unexamined $r$.