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A diol has two hydroxy groups. Its two groups can serve as joining ends in polyaddition; the rest of its molecule can already be a long chain.

Polyaddition is step-growth polymerization by joining reactions without elimination of small molecules. Compatible functional groups on different chain lengths remain eligible to join; the word addition alone does not imply chain-growth polymerization.^[ref]

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]