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Chemistry 1920

Über Polymerisation (On Polymerization)

Hermann Staudinger

Rubber, plastic and protein are each one giant molecule, not a heap of small ones.

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In depth · the introduction

For a century chemists assumed molecules came in one size: small. Staudinger insisted that some are gigantic — and that rubber, silk and plastic are each, in effect, one enormous molecule.

The big idea

Most molecules you meet in chemistry are tiny — a water molecule is just three atoms. Staudinger said that materials like rubber, cellulose and the early plastics are different in kind: each is built from thousands of small units locked end-to-end by strong chemical bonds into one immense chain molecule, what he later named a macromolecule. Stretched out, a single one might be tens of thousands of atoms long.

That sounds obvious now, but in 1920 it was heresy. The accepted explanation was that these substances were just lots of ordinary small molecules clinging together in clumps, like a snowball of loose flakes. Staudinger's claim was that there is no clump — the giant size is one real molecule, held by the same covalent bonds as any other.

How it came about

Staudinger was already a respected organic chemist, working at the ETH in Zürich, when he turned to the messy "colloidal" substances most chemists avoided. In a 1920 paper bluntly titled "On Polymerization", he laid out the case that polymerization is a normal chemical reaction stringing small units into long chains — then spent the next decade proving it against fierce resistance.

His strongest experiment was almost theatrical. If rubber were really a heap of small molecules held together by their double bonds, then chemically removing those double bonds — by adding hydrogen — should make it crumble into small pieces. Staudinger hydrogenated rubber, and it stayed rubbery and still behaved as a giant molecule. Solution viscosity gave him a second weapon: the longer the chain, the thicker the solution, in a regular way he turned into a ruler for molecular weight. At a now-famous 1926 meeting in Düsseldorf he faced a room of hostile colleagues; within a decade the evidence had won, and in 1953 he received the Nobel Prize.

Why it mattered

Almost everything made of plastic, rubber or synthetic fibre exists because we learned to treat these materials as chains we can design: make the chains longer, branch them, or cross-link them, and you tune strength, stretch and melting point. And the same idea reorganised biology — proteins, starch, cellulose and DNA are all macromolecules, long chains whose order and length carry their function.

A way to picture it

Think of a strung bead necklace versus a heap of loose beads. The old theory said rubber was a pile of separate beads sitting close together; pick it up and it would scatter. Staudinger said the beads are strung — one continuous thread runs through all of them, so it is a single object you can lift as one. Cut the forces between loose beads and the pile collapses; a strung necklace does not. Staudinger's hydrogen experiment did exactly that cutting — and the material held together, because it was a necklace all along.

Interactive polymer: choose the long-chain macromolecule or the loose-cluster aggregate, then slide how many units link up; the chain's molecular weight and solution viscosity climb steeply together while the cluster stays small and thin.

Where it sits

Nineteenth-century chemistry had mastered the small molecule — Kekulé's benzene ring and van 't Hoff's tetrahedral carbon, both elsewhere in this Library — but balked at the large. Staudinger extended structural chemistry to the giant molecule, and in doing so prepared the ground for understanding life's own polymers: the proteins, and the DNA double helix worked out a generation later.

The original document
Original source text
H. Staudinger · Berichte der deutschen chemischen Gesellschaft 53 (1920): 1073–1085 · DOI 10.1002/cber.19200530627
The thesis (summary)
Polymerization is a genuine chemical reaction. Many small unsaturated molecules — monomers — add to one another through their principal valences, so the product is a single large molecule: a chain of identical units joined by ordinary covalent bonds, not a physical aggregate.
Against the aggregate view
Staudinger sets his account against the prevailing idea that high-molecular substances (rubber, cellulose, the new resins) are colloidal clusters — many small ring molecules held together only by weak secondary ("association") forces. He argues the size is the molecule itself, not an artefact of clumping; the bonds along the chain are the same strong bonds as in any small organic molecule.
Examples and programme
He treats polymerization products such as polystyrene and polyoxymethylene (from formaldehyde), and points toward rubber, as long-chain molecules whose mass is the number of units times the unit mass. The paper is largely programmatic: it names the target — the chain molecule — and the work needed to prove it, which Staudinger and others would supply over the following decade through hydrogenation, end-group, osmotic, ultracentrifuge and X-ray studies.
[ … ]
The term "Makromolekül" (macromolecule) follows in Staudinger's 1922 papers; the quantitative viscosity–molecular-weight law follows in 1930. The 1920 paper is the opening manifesto of that programme.
Chemical Institute, ETH Zürich · 1920