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Molecular Weight of Polymers: Entanglements

Molecular weight of polymers is related to entanglements. Higher molecular weight polymers have longer polymer chains, which results in more entanglements between chains. Entanglements prevent the chains from sliding past one another and contribute to secondary bonding forces that associate chains together. Polymer crystallinity arises from the arrangement of molecular chains into repeating unit cells.

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73 views14 pages

Molecular Weight of Polymers: Entanglements

Molecular weight of polymers is related to entanglements. Higher molecular weight polymers have longer polymer chains, which results in more entanglements between chains. Entanglements prevent the chains from sliding past one another and contribute to secondary bonding forces that associate chains together. Polymer crystallinity arises from the arrangement of molecular chains into repeating unit cells.

Uploaded by

hanan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Molecular Weight of Polymers

Entanglements:

 It is simply the mutual wrapping of the polymer chains around each other.

 Higher molecular weight polymers imply longer polymer chains and longer polymer chains
imply more entanglements.

 When the polymers are highly entangled then


they resist sliding over each other.

 The effect of entanglements results in the


formation of secondary bonds or
intermolecular forces.

 Thus entanglements tend to keep the molecular chains associated together.


POLYMER CRYSTALLINITY

Figure 14.10 Arrangement


of molecular chains in a
unit cell for polyethylene.
(Adapted from C.W. Bunn,
Chemical Crystallography,
Oxford University Press,
Polymer Synthesis and Structure
 Addition Polymerization/Chain Polymerization/Free Radical Polymerization

 Step Polymerization/Condensation Polymerization

Functionality of Monomers:

In order for a monomer to polymerize,


 It must have at least two active chemical bond sites—called ‘Bifunctional Monomer’-
For such molecules, long and linear chains are formed.

 If have three active sites then called ‘Trifunctional Monomer’---For such molecules,
network structures are formed.
Polymer Synthesis and Structure
 Addition Polymerization/Chain Polymerization/Free Radical Polymerization

The steps for polymerization are

1) Initiation

2) Propagation

3) Termination
Polymer Synthesis and Structure
 Addition Polymerization/Chain Polymerization/Free Radical Polymerization

1) Initiation: Ethylene monomer


Polymer Synthesis and Structure
 Addition Polymerization/Chain Polymerization/Free Radical Polymerization

2) Propagation:
Polymer Synthesis and Structure
 Addition Polymerization/Chain Polymerization/Free Radical Polymerization

3) Termination:

It occurs by n = degree of
i) by addition of terminator free radical Polymerization (DP)
ii) by combining the growing chains together

+
Polymer Synthesis and Structure
 Step Polymerization/Condensation Polymerization

The joining of two molecules with the formation of a small by product molecule is called
Condensation.
Polymer Synthesis and Structure
 Step Polymerization/Condensation Polymerization For Nylon 66 (PA66)
Polymer Synthesis and Structure
 Step Polymerization/Condensation Polymerization For Nylon 66 (PA66)
Polymer Synthesis and Structure
 Step Polymerization/Condensation Polymerization For Nylon 66 (PA66)
Thermal Transitions in Polymers
Factors controlling the properties of polymers
 Chain Flexibility

 Interaction among the neighboring chains (Secondary bondings)

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