Chapter 4: Polymer Structures

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 What is the Polymer?

• Polymer = many mers

mer mer mer
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
Adapted from Fig. 14.2, Callister 6e.

• Naturally occurring polymers: From plants and animals

ex) wood, rubber, cotton, wool, leather, silk
proteins, enzymes, starches, cellulose

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 Hydrocarbon Molecules

• Most of polymers are “organic” in nature

™ Organic material: Material originated as a living organism
and therefore contains carbon. Or synthetic materials
containing carbon.

• Many organic materials are hydrocarbons (composed of C and H)

• Intramolecular bonds in hydrocarbons are covalent

™ C: 4 electrons participate in the covalent bonding
™ H: 1 electron participates in the covalent bonding

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 Single, Double, Triple Bonds
• Single bond: Each of the two bonding atoms contributes one electron
(sharing of only one pair of electrons)
H
H C H Methane (CH4)
H

• Double bond: Each of the two bonding atoms contributes two

electrons (sharing of two pairs of electrons)

H H
C C Ethylene (C2H4)
H H

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 Single, Double, Triple Bonds

• Triple bond: Each of the two bonding atoms contributes three electrons
(sharing of three pairs of electrons)

H C C H Acetylene (C2H2)

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 Saturated and Unsaturated Hydrocarbons
Unsaturated Hydrocarbon
• Molecules that have double or triple covalent bonds
• Each carbon atom is not bonded to the maximum (4) other atoms.
• Therefore, it is possible for another atom or group of atoms to
become attached to the original molecule
H H
H C C H Acetylene (C2H2) C C Ethylene (C2H4)
H H
Saturated Hydrocarbon
• All bonds are single bonds
• Therefore, no new atom may be joined without replacing
H
H C H Methane (CH4)
H
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 Paraffin Family

• Formula: CnH2n+2
H H
H C C H
H H
(CH2)n + 2H => CnH2n+2

• Intramolecular bond is strong (because it is covalent bonding)

• Intermolecular force: van der Waals bonds or weak hydrogen bonds

=> low melting and boiling points

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 Isomerism

• Same composition, but different atomic arrangement

• Ex: Butane (C4H10)

H
H C H
H H H H
H H
H C C C C H
H C C C H
H H H H H H H
normal butane isobutane
Boiling point: -0.5 C Boiling point: -12.3 C

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 Organic Radicals (Organic Groups)

• Groups of atoms that remain as a single unit

• Maintain their identity during chemical reactions

• Ex: CH3, C2H5, C6H5

H H H
H C H C C
H H H
methyl group (CH3) ethyl group (C2H5) phenyl group (C6H5)

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 Polymerization Process

H H H H
R + C C R C C
H H H H

H H H H H H H H

R C C + C C R C C C C
H H H H H H H H

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 Polyethylene

Angle: ~ 109°
Bond Length: ~0.154 nm
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Common Polymers

Polytetrafluoroethylene
(PTFE or Teflon)

Poly(vinyl chloride)
(PVC)

Polypropylene
(PP)

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 Classification

• Homopolymer: Composed of the same mer units

• Copolymer: Composed of two or more different mer units

H H
• Bifunctional monomer: two active bonds C C
H H

• Trifunctional monomer: three active bonds

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Distribution of Molecular Weights or Chain Lengths

• Number-average molecular weight

• Weight-average molecular weight
• Degree of polymerization
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Distribution of Molecular Weights or Chain Lengths

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 Degree of Polymerization

Degree of polymerization:
Average number of mer units in a chain n:

average molecular weight

n=
monomer molecular weight

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Molecular Shape

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 A Schematic of Single Polymer Chain

r is much smaller than the total chain length

The random coils and molecular entanglements are

responsible for characteristics of polymers. Ex: large
elastic extensions of rubber
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 Rotational Flexibility

• Some of the mechanical and thermal characteristics of polymers

are related to the rotational flexibility in response to applied
stresses or thermal vibrations.

• Rotational flexibility is dependent on mer structure and chemistry.

• Chain segment with a double bond (C=C) is rotationally rigid.

• A bulky or large side group of atoms restricts rotational movement.

Ex:

Polyethylene (PE) Polystyrene (PS)

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 Molecular Structure

Linear Branched

Crosslinked Network (three-dimensional)

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 Linear Polymers

• Flexible.

• Van der Waals or hydrogen bonding between the chains.

• Polyethylene, poly(vinyl chloride), polystyrene, poly(methyl

methacrylate), nylon, fluorocarbons.

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 Branched Polymers

• Results from side reactions that occur during the polymer

synthesis => results in a lowering of the polymer density.

• Polymers that form linear structures may also be branched.

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 Crosslinked Polymers

• Adjacent linear chains are joined together by covalent bonds.

• Crosslinking is achieved either during synthesis or by a

nonreversible chemical reaction at an elevated temperature.

• Crosslinking is often accomplished by additive atoms or

molecules that are covalently bonded to the chains.

• Ex: many rubbers

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 Network Polymers

• Trifunctional mer units form three-dimensional networks.

• A highly crosslinked polymer may be classified as a network

polymer.

• Ex: epoxies, phenol-formaldehyde.

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 Molecular Configurations

The regularity and symmetry of the side group arrangement

Head-to-Tail Configuration Head-to-Head Configuration

In most polymers, head-to-tail configuration predominates

(there often exists a polar repulsion between R groups in
head-to-head configuration

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Stereoisomerism (for head-to-tail configuration)
Isotactic Configuration

Syndiotactic Configuration

Atactic Configuration

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 Geometrical Isomerism

Cis Structure Trans Structure

cis-isoprene trans-isoprene

cis-polyisoprene is natural rubber

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Classification Scheme for Polymers

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 Plastics
If you look at each bottom of a plastic container, you are likely to see a recycle
symbol containing a number. The number in the middle of the recycle symbol
represents the kind of polymer from which the container is made.

In general, the lower the number, the greater the ease with which the material can
subsequently be recycled.

Number Abbreviation Polymer

1 PETE Polyethylene terephthalate (a polyester)
2 HDPE High density polyethylene
3 PVC Polyvinyl chloride
4 LDPE Low density polyethylene
5 PP Polypropylene
6 PS Polystyrene
7 Others

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 Thermoplastic and thermosetting
Classification according to behavior with rising temperature:
• Thermoplasts (thermoplastic polymers)
• Thermosets (thermosetting polymers)

1. Thermoplasts (thermoplastic polymers):

• Soften when heated and eventually liquefy and harden when cooled.
• Totally reversible and may be repeated.
• As the temperature is raised, secondary bonding forces are diminished so that
the relative movement of adjacent chains is facilitated.
• Irreversible degradation results when the temperature is raised to the point at
which the primary covalent bonds are broken.
• Relatively soft
• Ex: most linear polymers, polymers with some branched structures with
flexible chains

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 Thermoplastic and thermosetting

2. Thermosets (themosetting polymers)

• Become permanently hard when heat is applied and do not soften upon
subsequent heating.
• During initial heat treatment, covalent crosslinks are formed.
• These bonds anchor the chains together to resist the vibrational and rotational
chain motion at high temperature
• Crosslinking is extensive: 10-50% of the mer units are crosslinked.
• Only heating to excessive temperatures will cause degradation of polymer.
• Generally harder and stronger than thermoplastics.
• Most of crosslinked and network polymers
• Ex: vulcanized rubbers, epoxies, phenolic, polyester resins

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Copolymers

Random: Two different units are

randomly dispersed along the chain

Alternating: Two mer units alternate chain

positions

Block: Identical mers are clustered

in blocks along the chain

Graft: Homopolymer side branches of

one type are grafted to homopolymer
main chain

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 Polymer Crystallinity
• The crystalline state may exist in polymer materials.

• Packing of ordered molecular chains.

• Molecular substances having small molecules are normally either

totally crystalline or totally amorphous. (Ex: water, methane)

• Often only partially crystalline (semicrystalline): having crystalline

regions dispersed within the remaining amorphous materials.
• Amorphous region: any chain disorder or misalignment (twisting,
kinking, coiling)
• By comparison: Metal: mostly totally crystalline, Ceramics: either
totally crystalline or totally non-crystalline.

The degree of crystallinity of a polymer depends on the rate of

cooling during solidification and the chain configuration

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Unit Cell of Polyethylene

Orthorhombic geometry
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 Degree of Crystallinity

• The density of a crystalline polymer will be greater than an amorphous

one of the same material and molecular weight, since the chains are
more closely packed together.

• The degree of crystallinity by weight may be determined from accurate

density measurements, according to

ρc ( ρ s − ρa )
% crystallinity = ρ s ( ρc − ρa ) × 100
Where ρs is the density of a specimen for which the percent
crystallinity is to be determined,
ρa is the density of the totally amorphous polymer,
ρc is the density of the perfectly crystalline polymer.

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 Fringed-Micelle Model
(crystallites, or micelles)

A single chain molecule might pass through several crystallites

as well as the intervening amorphous regions.
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 Chain-Folded Model

• Grown from dilute solution.

• Each platelet consists of a number of molecules.
• Average chain length is much greater than the thickness of the platelet.

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 Chain-Folded Model

TEM image of a polyethylene single crystal (multilayered structure).

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 Spherulites
Thickness: ~ 10nm

TEM Image of Spherulite

Structure of Natural Rubber.

• Grow from melts to spherical shape.

• The polymer analogue of grains in polycrystalline metals and ceramics.
• Ex: Polyethylene, polypropylene, poly(vinyl chloride),
polytetrafluoroethylene, nylon
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 Spherulites of Polyethylene

Spherulite Structure of Polyethylene: A transmission

photomicrograph (using cross-polarized light)

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