Addition Polymerisation

Summary: Addition polymerisation is the process where many small unsaturated monomer molecules (containing C=C double bonds) join together to form a long polymer chain without producing any byproducts. Tags: igcse chemistry organic-chem polymers Created: 2026-07-14 Last Updated: 2026-07-23


Definition

Addition polymerisation is the reaction in which many small unsaturated monomers (alkenes with C=C double bonds) join together to form a very long saturated polymer chain. No other products are formed — all the atoms from the monomer end up in the polymer.

The process requires:

  • High pressure
  • A catalyst (often a Ziegler-Natta catalyst or an organic peroxide initiator)
  • Heat (moderate temperature)

What Happens

  1. The C=C double bond opens up
  2. Monomers link together by forming single covalent bonds between carbon atoms
  3. The polymer backbone is a chain of carbon-carbon single bonds
  4. The reaction continues until the chain is terminated

Key point: The double bond breaks open → single bonds form between monomers. Think of it as “unzipping” the double bond to “zip” monomers together.

Addition Polymers You Need to Know

Poly(ethene) — commonly called polythene

  • Monomer: Ethene (C₂H₄), CH₂=CH₂
  • Repeating unit: —CH₂—CH₂—
  • Properties: Flexible, low density (LDPE) or rigid, high density (HDPE)
  • Uses: Plastic bags (LDPE), bottles and pipes (HDPE), cling film

Poly(propene) — commonly called polypropylene

  • Monomer: Propene (C₃H₆), CH₂=CH—CH₃
  • Repeating unit: —CH₂—CH(CH₃)—
  • Properties: Tough, flexible, higher melting point than poly(ethene)
  • Uses: Rope, carpet fibres, food containers, medical syringes, car bumpers

Poly(chloroethene) — commonly called PVC

  • Monomer: Chloroethene (C₂H₃Cl), CH₂=CHCl
  • Repeating unit: —CH₂—CHCl—
  • Properties: Rigid (uPVC) or flexible (PVC with plasticiser added)
  • Uses: Window frames, drainpipes (uPVC), electrical cable insulation (flexible PVC)

PTFE — Poly(tetrafluoroethene)

  • Monomer: Tetrafluoroethene (C₂F₄), CF₂=CF₂
  • Repeating unit: —CF₂—CF₂—
  • Properties: Non-stick, heat resistant, very low friction
  • Uses: Non-stick pan coating, plumber’s tape, chemical container linings

From Monomer to Polymer

General equation for addition polymerisation of any alkene:

n(CH₂=CHX) → —(CH₂—CHX)—ₙ

Where:

  • n = a very large number (typically 10,000–100,000+)
  • X = H (ethene), CH₃ (propene), Cl (chloroethene), F (tetrafluoroethene)

Drawing Addition Polymers at IGCSE

The examiner wants to see:

  1. The repeating unit shown in brackets with extension bonds: [—CH₂—CHX—]ₙ
  2. Extension bonds through the brackets
  3. No double bonds in the polymer backbone
  4. The ‘n’ subscript outside the brackets

Example — Poly(ethene):

    H H
    | |
—[—C—C—]—ₙ
    | |
    H H

Comparison: Addition vs Condensation Polymerisation

FeatureAdditionCondensation
MonomerUnsaturated (has C=C)Two functional groups per monomer
Byproduct?NoneSmall molecule (H₂O, HCl) eliminated
Polymer backboneC—C chain onlyMay contain O, N in backbone
ExamplesPoly(ethene), PVC, PTFENylon, PET, proteins
Mass of polymer= mass of all monomers< mass of all monomers (byproduct lost)

Key Facts

  • Monomers must have C=C double bonds (alkenes)
  • Double bond opens up → monomers join by single covalent bonds
  • No byproducts — all atoms end up in the polymer
  • Polymer is saturated (no double bonds in backbone)
  • Repeating unit formula = same as monomer (atoms just rearranged)
  • Examples: poly(ethene), poly(propene), PVC (poly(chloroethene)), PTFE
  • Addition polymers are non-biodegradable → environmental/pollution concerns