Step-growth polymerization

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]

Use an ideal feed in which every starting molecule has exactly two suitable functional groups: either one $A$ and one $B$, or two $A$ groups mixed with two $B$ groups. Only an $A$–$B$ pairing can form a joining chemical bond. Assume no loss of feed-derived material, no splitting of chains, no competing consumption of the counted functional groups, no branching, and no cyclization in step-growth polymerization. Linear here describes connectivity; a chain can bend in space. Small byproducts of polycondensation do not enter the chain-bearing molecule count.

Let $N_0$ count all initial feed molecules, $J$ the number of intermolecular joins, and $N$ all remaining chain-bearing molecules, including unreacted monomers. Each join turns two molecules into one, so $N=N_0-J$ exactly. If chain $i$ contains $j_i$ feed-derived monomeric units, conservation gives ${\sum }_{i=1}^N{j}_i=N_0$. Consequently the number-average degree of polymerization isThis is a count of both feed species' monomeric units, rather than a count of interior constitutional repeating units. For $AA+BB$ chemistry an interior repeat often contains two feed-derived units, as explained in monomer. Equal functional group reactivities are not needed for this bookkeeping at a specified $J$; predicting a time course or a chain-length probability distribution requires additional assumptions.

For the figure's eight $AB$ feed molecules, three joins can give lengths $(2,3,1,1,1)$, so $N=5$ and $X_n=8/5$. Joining the first two chains gives $(5,1,1,1)$: the incorporated total stays eight, $N$ becomes four, and $X_n=2$. A graph makes the bookkeeping visible: each starting monomer molecule is a vertex of a graph, and each intermolecular joining chemical bond connects two previously distinct connected components of a graph. The connected pieces are the counted molecules.

In a balanced bifunctional feed there are initially $N_0$ $A$ groups and $N_0$ $B$ groups. Define the functional-group conversion in step growth by $p=J/N_0$: the reacted fraction of either group type. Each join consumes one of each. Therefore $N=N_0(1-p)$. In the eight-$AB$ example, three joins give $p=3/8$ and four give $p=1/2$. In the latter state only three of eight starting monomer molecules remain isolated: their disappearance fraction is $5/8$, different from $p=1/2$. Neither this group-based $p$ nor disappearance of isolated monomers is the incorporated-feed fraction in the ideal living polymerization count.

With unequal initial counts $A_0\le B_0$, this article always uses $p=J/A_0$, the conversion of the limiting $A$ groups. The reacted fraction of $B$ groups is $J/B_0=rp$, where $r=A_0/B_0$. The fraction of all initial functional groups consumed is $2J/(A_0+B_0)=2rp/(1+r)$. At nonzero conversion these three fractions coincide only at $r=1$. Naming the measured group type prevents an apparently correct equation from using the wrong conversion.

The balanced Carothers equation follows immediately from linear step-growth molecule count and functional-group conversion in step growth:The same Carothers equation extends to unequal group counts once the limiting-group convention is specified.^[ref]

For an original balanced feed of $2000$ monomer molecules, $1900$, $1960$, and $1990$ intermolecular joins give $p=0.95$, $0.98$, and $0.995$. The remaining counts are $100$, $40$, and $10$, hence number-average degree of polymerization values $20$, $50$, and $200$. The last thirty joins quadruple the average even though they consume only another $1.5\%$ of the initial groups of either type. These are exact synthetic counts, not experimental measurements.

The derivative $d{X}_n/dp=(1-p{)}^{-2}$ explains the sensitivity: near $p=0.99$, an absolute conversion uncertainty of $0.001$ changes the predicted degree of polymerization substantially. The exact balanced values at $p=0.989$ and $0.991$ are approximately $90.9$ and $111.1$, instead of $100$. An instrument reporting rounded “complete conversion” cannot distinguish those chain lengths. In a finite no-ring system, even one chain retains two ends; the maximum $p$ is $1-1/N_0$ and $X_n=N_0$. The formal divergence at $p=1$ is a large-system limit, not an infinite chain in a finite flask.

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 $r$.

In cyclization in step-growth polymerization, compatible functional groups on the same chain react and close it into a ring. They consume groups without merging two molecules. If $R$ ring-closing events and $J$ intermolecular joins occur in an otherwise balanced bifunctional feed, the group conversion is $p=(J+R)/N_0$, while $N=N_0-J=N_0(1-p)+R$. ThusFor example, an $AB$ dimer can close its remaining $A$ and $B$ ends: two group pairings have occurred among two starting monomer molecules, giving $p=1$, but the resulting single cyclic molecule has only two monomeric units. This counterexample shows exactly where the linear Carothers equation fails. Rings have no chain ends, so counting every chain-bearing molecule as two ends also fails.

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]

An experimental comparison joined a two-ended diol chain, HOPCLOH, with a bifunctional isocyanate, at reported isocyanate-to-diol ratio $1.14:1$. The researchers used oven-dried $25\mathrm{mL}$ round-bottom flasks and an IKA RET magnetic hotplate with a metal carrier. They varied solvent, concentration, reaction temperature ($50$ or $61{}^{\circ }\mathrm{C}$), and duration ($1$ or $8\mathrm{h}$).^[ref]

A Bruker $500\mathrm{MHz}$ NMR spectroscopy instrument measured residual hydroxy group-adjacent signal relative to an ester signal. Independently, size-exclusion chromatography used ResiPore columns at $70{}^{\circ }\mathrm{C}$, a refractive-index detector, and polystyrene calibration. Figure 8 reports sharply increasing apparent number-average molar mass beyond the reported conversion $0.95$. A deliberately water-exposed isocyanate comparison reproduced a $1625\mathrm{c}{\mathrm{m}}^{-1}$ infrared spectroscopy band assigned to urea-containing products. The authors warn that tiny residual NMR spectroscopy signals reduce integration precision.^[ref]

The inference is increasing chain size alongside depletion of reactive groups, consistent with step-growth polymerization. It is not an exact measurement of $X_n$ in the toy model. The feed contains already extended diol chains: counting their constituent repeat units differs from counting each feed molecule as one unit. Their varying molar masses, calibration against a different polymer, residual starting material, and competing chemical reactions further obstruct a direct conversion-to-$X_n$ substitution. Report which functional groups the conversion readout measures before comparing it with stoichiometric imbalance in step growth.

Useful proposed controls, distinct from the reported water comparison, are pre-reaction spectra and matched mixtures omitting each joining partner in turn. Keep solvent, heating, and signal normalization matched. Disappearance of an isocyanate signal in the omitted-diol control would reveal competing consumption rather than establish chain joining. Agreement between residual-group and independently calibrated chain-size readouts is stronger evidence than calculating both quantities from the same Carothers equation.

Polycondensation is step-growth polymerization in which joining reactions eliminate small molecules. Its chain-bearing molecule count excludes those byproducts; otherwise two chains joining while releasing one small product would misleadingly appear to conserve the counted population.^[ref]

Formation of Si–O–Si linkages from silanol groups, with elimination of water or another small molecule according to the reacting functional groups.