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Polypropylene (PP)
indicates how broad the differences in the chain lengths of the constituent
polymer molecules in a given sample are; polydispersity; heterogeneity index
If polymer molecules are of the same size (e.g. protein): ratio = 1
For synthetic polymers, ratio > 1
Molecular weight distribution
curve
Nylon 11 has the following structure
Xn and n(DP) define the same quantity for two slightly different entities
DP for a single molecule is n; polymer mass is composed of millions of molecules,
each of which has a certain degree of polymerization (Xn)
butadiene
bifunctional
butadiene
tetrafunctional
at right conditions (high temperature; cross-linking) the remaining double bonds might
undergo addition reaction (w/c will result to tetrafunctionality)
Latent functionality – property of monomer where its functional groups react at
different conditions
Classification of Polymers by
Structure: Functionality
What if two monomers are both monofunctional?
reactive groups on the acid and alcohol are used up completely; product ester is
incapable of further esterification reaction
What if two monomers are both bifunctional?
ester is itself bifunctional, being terminated on either side by groups that are capable
of further reaction
same holds for polyfunctional molecules
To generate a polymer through the repetition of elementary units, monomer/s
must be at least bifunctional
Classification of Polymers by
Structure
Poly(methyl methacrylate)
Pendant groups – substituent groups attached to the main chain of skeletal atoms
(-CH3, -Cl, -CN, etc); they could change properties of polymers (e.g. solubility)
Cross-linked polymers – generally insoluble; swelled by liquids; highly stable, rigid, high-melting
Classification of Polymers by
Structure Ladder polymer - consists of two
parallel linear strands of molecules with
a regular sequence of crosslinks
have only condensed cyclic units in the
chain; commonly referred to as double-
chain or double-strand polymers
polymerization of aromatic
dianhydrides such as pyromellitic
dianhydride or aromatic tetracarboxylic
acids with orthoaromatic tetramines like
1,2,4,5-tetraaminobenzene
more rigid than that of conventional
linear polymers
exceptional thermal, mechanical, and
electrical behavior
poly(imidazopyrrolone)
thermal stability - requires that two bonds must
be broken at a cleavage site in order to disrupt the
overall integrity of the molecule
Show the polymer formed by the reaction of the
following monomers. Is the resulting polymer linear or
branched/cross-linked?
Show the polymer formed by the reaction of the
following monomers. Is the resulting polymer linear or
branched/cross-linked?
Show the polymer formed by the reaction of the
following monomers. Is the resulting polymer linear or
branched/cross-linked?
Show the polymer formed by the reaction of the
following monomers. Is the resulting polymer linear or
branched/cross-linked?
linear polymer
Classification of Polymers by
Structure: Crystalline polymers
• when polymers are cooled from the molten state or
concentrated in a solution, molecules are often attracted to
each other and tend to aggregate as closely as possible into a
solid with the least possible potential energy
• for some, individual chains are folded and packed regularly in
an ordered fashion
• impossible for chains to fit in a perfect arrangement (e.g. low
molecular-weight polymers) degree of crystallinity
• PE and PET (crystalline)
Polyethylene
repeating unit and the structural unit of a polymer are not necessarily the same
Nylon 6,6 and PET - repeating units composed of more than one structural unit; still
homopolymers
Classification of Polymers by
Structure: Copolymer systems
• Random copolymer – repeating units arranged
randomly
• Alternating copolymer - ordered (alternating)
arrangement of 2 repeating units along the polymer
chain
• Block copolymer – consists of relatively long
sequences (blocks) of repeating unit
• Graft copolymer – sequences of one monomer
“grafted” onto the backbone of another monomer
type
Classification of Polymers by
Structure: Copolymer systems
random copolymer
alternating copolymer
block copolymer
graft copolymer
Classification of Polymers by Structure:
Fibers, Plastics, or Elastomers
• Fibers: linear polymers w/ high symmetry and high intermolecular
forces (secondary valence forces; van der Waals, hydrogen bond,
dipole bonds) that result usually from the presence of polar groups;
high modulus, high tensile strength; moderate extensibilities (less
20%)
• Elastomers: polymer molecules w/ irregular structure; weak
intermolecular attractive forces; very flexible polymer chains; in
absence of applied tensile stress, molecules assumed coiled shape;
high extensibility (up to 1000%) from w/c they recover rapidly upon
removal of imposed stress; low initial modulus in tension; stiffen
when stretched
• Plastics: fall between fibers and elastomers; polyamides and
polypropylene (usually classified as plastics) can also be made as
fibers; not clear boundary definition
Classification of Polymers by
Polymerization Mechanism
• old classification – addition, condensation
• Addition polymers – sequential addition of one
bifunctional or polyfunctional monomer to growing
polymer chains; usually very fast
poly(vinyl chloride)
polyamides (nylon)
Nylon 6,6 – poly(hexamethylene
adipamide)
Nylon 6 – poly(ω-aminocaproic
acid)
Classification of Polymers by Polymerization
Mechanism: Inconsistency with old classification
• Certain polymer molecules could be prepared
by one more than mechanism
For PE, 2nd reaction is neither
addition nor condensation