TE 570 Polymer Physics

Chapter 2. Microstructures

Xiangwu Zhang

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Outline
 Homopolymers
 Configurations and Conformations
 Stereochemistry of Repeating Units
 Isomerism of Repeating Units
 Confirmation, Size, Shape, and flexibility
 Microstructure-Property Relationships
 Copolymers
 Skeletal Structure (Organization of Polymer
Chains)
 Characterization Methods
 Special Topic – Natural Polymer Fibers
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Homopolymers

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Head-to-Head and Head-to-
Tail Configurations
 Head-to-Tail (√ most cases)

 Head-to-Head

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 Configurations: Structure-
Property Relationship
 Poly-isobutylene (also-called butyl rubber, a synthetic rubber, or
elastomer. It is only rubber that's truly gas impermeable, that is, it's the
only rubber that can hold air for long periods of time. )
 It is often copolymerized with a little bit (say, around 1 or 2 %) isoprene

•Head-to-Tail (√ rubber): • Head-to-Head:

Tg = -61 oC Tg = 87 oC
Tm = 5 oC (crystallize only Tm = 187 oC
under stress) 5
Stereochemistry
 Chiral centers
The term chiral (pronounced /’kairƏl̩ /) is used to describe an object which
is non-superimposable on its mirror image


configuration of polymer chains (tacticity)

Isotactic Syndiotactic Atactic 6

Stereochemistry: Structure-
property relationships

Crystallizable

Crystallizable

Amorphous
only
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Stereochemistry of several
commercial polymers

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cis and trans Configurations:
geometric isomerism
 cis configuration arises when substituent groups are on the
same side of a carbon-carbon double bond.
 Trans refers to the substituents on opposite sides of the double
bond

 Both cis and trans are crystallizable, but their mixtures suppress
crystallization
 Which polybutadiene has lower Tm? cis or trans?

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Substitutional Isomerism
 1,2 versus 1,4 addition

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 Configurations and Conformations
 Configurations (refers to the order that is determined by
chemical bonds. The configuration of a polymer cannot
be altered unless chemical bonds are broken and
reformed)
 Head-to-Tail vs. Head-to-Head

 Isotactic vs. Syndiotactic vs. Atactic

 Cis vs. Trans

 1,2 vs. 1,4 addition

 Conformations (refers to order that arises from the

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rotation of molecules about the single bonds)
Conformation-Rotations of a
Single Bond

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 Conformation

N is typically 1,000-10,000 bonds

Number of conformations = 310,000 = 104,800
Bond rotational relaxation times =10-10s
Rate of transition between conformation 1010 conf/s
Time required for 104,800 conformations = 3x104782 yrs
Our universe is 2 x1010 yrs old
Polyethylene Has not had time to become bored!!! 13
Why study conformation?
 What properties are related to chain
conformation?

 When one needs to concern about

chain conformation?

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Conformation: two extremes

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 Conformation: two extremes
 Size:

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Structure-Property Relationships:
Backbone structure (1)
 Single bond

 -Si-O- -C-N- -C-O- -C-C-

 Benzene ring

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Structure-Property Relationships:
Backbone structure (2)
 Isolated double bonds

 Conjugated double bonds

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Structure-Property Relationships:
Backbone structure (3)
 Cellulose (hydrogen bond)

 Protein (helico-, hydrogen bond)

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Structure-Property
Relationships: Side Chains
 Polar group  poor flexibility
PP

 More polar group  poorer flexibility

 Polar group distribution

 Non-polar group: size

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Structure-Property Relationships:
Branches, Crosslinking, and chain length
 Branches  poor flexibility

 Crosslinking: 2-3%  no much impact

>30%  significantly lower flexibility

 Longer Chain length  ???

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Structure-Property Relationships:
Intermolecular force and crystallization
 Intermolecular force

 Crystallization

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Other Factors Affecting
Polymer Chain Flexibility
 Temperature  good flexibility
e.g., Polystyrene, polybutadiene

 Applied Force  time scale of observation

 Solvent

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 Homopolymers
 Configurations and Conformations
 Stereochemistry of Repeating Units
 Isomerism of Repeating Units
 Confirmation, Size, Shape, and flexibility
 Microstructure-Property Relationships
 Copolymers
 Skeletal Structure (Organization of Polymer
Chains)
 Characterization Methods
 Special Topic – Natural Polymer Fiber
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 Copolymers

Two or more repeating units

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Block Copolymers

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 Homopolymers
 Copolymers
 Skeletal Structure (Organization of
Polymer Chains)
 Characterization Methods

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Skeletal Structure (Chain
Architectures)

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 Skeletal Structure: Branched
Polymers
 Not all polymers are
linear. Sometimes,
there are chains which
are comparable in
length to the backbone
chain
 Some thermoplastic
polymers, like
polyethylene, can be
made in linear or
branched

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 HDPE vs. LDPE
LDPE
HDPE

 The branching increases the volume and thus

reduces the density of the polymer.
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LDPE, HDPE, LLDPE, and
ULDPE

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 Skeletal Structure: Star
Polymers
 Sometimes the ends of
several polymer chains
are joined together at a
common center

 Polymers like this are

called star polymers

 They're often used as

additives or as coating
materials
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 Skeletal Structure: Dendrimers
 Sometimes there is no
backbone chain at all
 Sometimes a polymer is built
in such a way that branches
just keep growing out of
branches and more branches
grow out of those branches
 These are called dendrimers,
from the ancient Greek word
for "tree“
 They are different from star
polymers

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Skeletal Structure: Dendrimers

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 Skeletal Structure: Cross-
linked Polymers
 Sometimes, both ends of the
branch chains are attached to the
backbone chains of separate
polymer molecules
 If enough branch chains are
attached to two polymer
molecules, it can happen that all
of the polymer backbone chains in
a sample will be attached to each
other in a giant 3-D network
 This is what happens in certain
hydrogels, some polyelectrolytes,
rubber, silicone and certain
polyurethanes
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Others

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Others

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 Characterization Methods
Molecular Characterization

Shape
Chemistry Size
Chain Twisting, Structure
Repeat unit composition Molecular Weight
Entanglement, etc

Linear Branched Crosslinked others

Configurations

Head-to-Tail Isotactic Cis 1,2 addition

vs. vs. vs. Vs.
Head-to-Head Syndiotactic Trans 1,4 addition
vs.
Atactic 38
Chemical Methods

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Physical Methods

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 Homopolymers
 Configurations and Conformations
 Stereochemistry of Repeating Units
 Isomerism of Repeating Units
 Confirmation, Size, Shape, and flexibility
 Microstructure-Property Relationships
 Copolymers
 Skeletal Structure (Organization of Polymer
Chains)
 Characterization Methods
 Special Topic – Natural Polymer Fibers
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 Natural Polymer Fibers

 Natural fibers
 More complex than synthetic
fibers
 Cellulosic building units
 Cotton
 Linen
 Flax
 Hemp
 Wood
 Aminoacid building units
 Wool
 Vicuna
 mohair
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 Cellulose
 Cellulose
 Glucose rings joined
together
 Cotton 100% cellulose beta linkages
 Wood 50% cellulose
(can make paper, but no
fibers)
 Starch
 Glucose rings joined
together
 Water soluble

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alpha linkages
 Cellulose (cont’d)

 -OH: polar group can form hydrogen

bonds, hydrophilic
 Glucose ring structure: provide stiffness
to chain

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 Natural Cellulose
 Cotton: molecules oriented at 25-30o to
axis

 Jute, flax: molecules parallel to axis (~6o)

Jute is a long, soft, shiny vegetable fiber Flax fibers are amongst the oldest fiber
that can be spun into coarse, strong crops in the world. It is stronger than
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threads (very cheap) cotton fiber but less elastic.
 Regenerated Cellulose
 Rayon: some (no more than 15%) hydrogens of the hydroxyl
groups have been replaced.

 Acetate: many (less than 92 %, but at least 74%) hydrogens of

the hydroxyl groups have been replaced by -CH3COO groups.
 Triacetate: most (no less than 92 %) hydrogens of the hydroxyl
groups have been replaced by -CH3COO groups. 46
Proteins - Polypeptides
Peptide linkage

 Proteins are one of many types of natural

polymers, and they are the most versatile by
far. You name it, proteins do it. What can
proteins do? What can't they do!
 They can be catalysts. Some proteins,

called enzymes, make certain chemical

reactions in your body take place up to
a million times faster than they would
without enzymes.
 One protein called hemoglobin is found

in your blood, and carries oxygen from

your lungs to your cells.
 Another protein called collagen is a

strong and tough material that makes

up your skin, hair, and fingernails.

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 Aminoacids

• Inmonomers
your body, these proteins are made from
called amino acids, like this:

• There are twenty different amino acids.

Each one has a different R' group. Also,
each protein has a specific sequence of the
different amino acids in it. This sequence
determines the properties of the protein.

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Proteins
Wool Silk
R' 20 different types 4 main different types

complex structure simple structure

12 % cysteine 0% cysteine
-CH2-S-S-CH2-
(like rubber)*

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