Chapter 4
Chain or (addition) Polymerisation
إعداد الدكتورة :سارة عبدهللا سعيد القرني
أستاذ الكيمياء العضوية المساعد
قسم الكيمياء – كلية العلوم
جامعة جدة 1
Chain Polymerisations
General Characteristics:
Each polymer chain grows fast. Once growth stops, the chain is no longer reactive
Chain reaction initiated by an external source (radiation, initiator or catalyst)
Growth of a polymer chain is caused by a kinetic chain of reactions
Chain reaction proceeds via monomer addition to an Active Centre
Active Centre can be a free-radical, anion, cation or polymer-catalyst bond
Chain Polymerisations are particularly useful for vinyl monomers
CH2 CH
where X = -OCOCH3 -CN -CH=CH2
X Also
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-Cl -COOCH3 Methacrylates
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Chain-growth polymers, also known as addition
polymers, are made by chain reactions
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Step-growth polymers, also called condensation
polymers, are made by combining two molecules by
removing a small molecule
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Chain-Growth Polymers
Chain-growth polymers proceed by one of three
mechanisms:
• radical polymerization
• cationic polymerization
• anionic polymerization
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Consider ‘free radical’ active centre first:
Advantages of free radical polymerization
Very robust technique
Applicable to a range of (functional) vinyl monomers
Wide range of operating conditions are possible
Works well in water, e.g. emulsion polymerization
Disadvantages of free radical polymerization
Poor selectivity (radicals are very reactive species)
Relatively poor control over polymer product in terms of its
MWD, architecture, stereochemistry, etc.
(i) Chemical initiators
Free-radicals usually generated by: (ii) UV radiation (photolysis)
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Two Common Classes of Chemical Initiators
Both classes provide unimolecular decomposition and first-order kinetics
(1) Peroxides (2) Azo compounds
Persulfate: S2O82- 2 SO4.- Sulfate radical anion
The above characteristic temperatures indicate the ‘10 hour’ half-lives:
e.g. 50 % of BPO initiator is decomposed to radicals after 10 h at 65 oC
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Radical Polymerization
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The molecular weight of the polymer can be controlled by
a process known as chain transfer
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Chain-growth polymerization of monosubstituted
ethylenes exhibits a marked preference for head-to-tail
addition
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Head-to-tail addition of a substituted ethylene results in a
polymer in which every other carbon bears a substituent
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Branching of the Polymer Chain
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Branched polymers are more flexible
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Cationic Polymerization
the alkene monomer
reacts with an electrophile
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The carbocation intermediates formed during
polymerization can undergo rearrangement
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Monomers that are best able to undergo cationic
polymerization are those with electron-donating
substituents
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Anionic Polymerization
Nonterminated chains are called living polymers
The chains remain active until they are killed 24
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