TE 570 Polymer Physics
Chapter 2. Microstructures
Xiangwu Zhang
1
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
2
Homopolymers
3
Head-to-Head and Head-to-
Tail Configurations
Head-to-Tail (√ most cases)
Head-to-Head
4
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
7
Stereochemistry of several
commercial polymers
8
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?
9
Substitutional Isomerism
1,2 versus 1,4 addition
10
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
11
rotation of molecules about the single bonds)
Conformation-Rotations of a
Single Bond
12
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?
14
Conformation: two extremes
15
Conformation: two extremes
Size:
16
Structure-Property Relationships:
Backbone structure (1)
Single bond
-Si-O- -C-N- -C-O- -C-C-
Benzene ring
17
Structure-Property Relationships:
Backbone structure (2)
Isolated double bonds
Conjugated double bonds
18
Structure-Property Relationships:
Backbone structure (3)
Cellulose (hydrogen bond)
Protein (helico-, hydrogen bond)
19
Structure-Property
Relationships: Side Chains
Polar group poor flexibility
PP
More polar group poorer flexibility
Polar group distribution
Non-polar group: size
20
Structure-Property Relationships:
Branches, Crosslinking, and chain length
Branches poor flexibility
Crosslinking: 2-3% no much impact
>30% significantly lower flexibility
Longer Chain length ???
21
Structure-Property Relationships:
Intermolecular force and crystallization
Intermolecular force
Crystallization
22
Other Factors Affecting
Polymer Chain Flexibility
Temperature good flexibility
e.g., Polystyrene, polybutadiene
Applied Force time scale of observation
Solvent
23
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
24
Copolymers
Two or more repeating units
25
Block Copolymers
26
Homopolymers
Copolymers
Skeletal Structure (Organization of
Polymer Chains)
Characterization Methods
27
Skeletal Structure (Chain
Architectures)
28
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
29
HDPE vs. LDPE
LDPE
HDPE
The branching increases the volume and thus
reduces the density of the polymer.
30
LDPE, HDPE, LLDPE, and
ULDPE
31
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
32
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
33
Skeletal Structure: Dendrimers
34
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
35
Others
36
Others
37
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
39
Physical Methods
40
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
41
Natural Polymer Fibers
Natural fibers
More complex than synthetic
fibers
Cellulosic building units
Cotton
Linen
Flax
Hemp
Wood
Aminoacid building units
Wool
Vicuna
mohair
42
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
43
alpha linkages
Cellulose (cont’d)
-OH: polar group can form hydrogen
bonds, hydrophilic
Glucose ring structure: provide stiffness
to chain
44
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
45
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.
47
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.
48
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)*
49