INTRODUCTION TO POLYMERPHYSIC

KULIAH III
TEKNOLOGI POLIMER MAJU

AKREDITASI INSTITUSI

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 POLYMERS IN THE SOLID STATE

I. STRUCTURE OF POLYMERS
To understand the behaviour of polymers in the solid state we have to know as much as possible about the chemical
structure of the polymer.

1.Constitution of Polymers
• Constitution describes the structure elements of polymers

2.Configuration
• Configuration describes those arrangements of atoms that can not be altered except by breaking bonds.

3.Conformation
• Conformations are arrangements, which are derived from the rotation of atoms around single bonds

4.Molecular Weight
• 1

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 1. Constitution of Polymers
Constitution describes the structure elements of polymers

1.1 Constitution of the polymer chain (polymer backbone)

Polymer chains are divided into

Isochains, homochains (chain consist of just one atom)

R R R R Example:
polyethylene
Polystyrene
poly methylacrylate

heterochains (polymer build up from more than one atom)

Examples:
Polyamide
X X Polyester
Polyurethane
Polyethylene oxide

Isochain (homochain) polymers are normally made with chain reaction, 2

heterochain polymers are made with step reaction (with some exceptions)

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 1.2 Building blocks of polymers

Homopolymer: Polymer, which consists of a single monomer species (IUPAC

Definition)

Styrene Repeating unit of polystyrene

Copolymer: Polymer, which is build up from more than one monomer.

CN
CN co
n m

acrylonitrile styrene 3

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Alternating copolymer: the monomers alternate regularily along the chain

A-B-A-B-A-B-A-B Poly (A-alt-B)

Random copolymer: no regularity of monomer sequences (most common copolymer)

A-A-B-A-B-B-B-A-A-B-A-B-A-A- Poly (A-ran-B) 2 1 1 3 2

1 1 1 2
Sequence: Section of same building blocks (monomers): Monade, Diade, Triade

Block copolymer: one sequence follows another

A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B Poly (A-block-B)

Graft copolymer: a polymer is grafted on a backbone

A-A-A-A-A-A-A-A-A-A-A-A-A Poly (A-g-B) B B
B B 4
B B

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 We can now continue using three different monomer A, B and C: Terpolymers

random

block

Important copolymers

Acrylonitrile-Butadiene-Styrene (ABS)

CN

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 Acrylonitril-styrene (SAN)

CN

Used for electric/ electronic parts

Poly(ethylene oxide)-b-poly(propylene oxide) (Pluronics, Brij)

CH3

CH2 CH2 O b CH2 CH O Used for biomedical applications

m m

We will learn later on why copolymers have such interesting

properties!

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 1.3. Polymer architecture
Single polymer chains can be connected with each other forming more complex
polymer architectures.

Linear chains

Synthesis of linear polymers

R1 R1
H2
Prepared with chain reaction: H2C C C

R2 n
R2

Or with step reaction:

O O O O
H+
R1 HO R2 OH R1 H2O

HO OH HO O R2 OH

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 Branched polymers
Branched polymers are still discrete molecules (in contrast to networks)

Special branched polymers:

Comb polymer: Star polymer:

Side arms have roughly the arms are connected at a single point at the
same length and branches are centre of the polymer (core)
distributed along the main
chain (backbone)

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 Synthesis of branched polymers

1.Side effect: back biting during polymerisation

Example: LDPE
CH2 CH2
CH CH2
CH2 CH2 CH2 CH2 CH CH2 CH2 CH2 CH3
H CH2
CH2

Formation of a transient six-membered ring

2. Addition of a multifunctional compound with a functionality f>2

Chain reaction:

Crosslinker

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 3. Subsequent crosslinking of polymer chains

crosslinker

The amount of crosslinker and its functionality determines the branching

density
High crosslinker concentration formation of insoluble networks

Note: Star polymers or comb polymers are normally prepared with other
methods (ionic polymerisation, ring-opening polymerisation, controlled radical
polymerisation)

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 Vulcanisation: Important Crosslinking method in industry
Discovery by Goodyear (1839): transforms elastomer polymer from a weak mass into
a strong, elastic, tough rubber
Originally done with sulfur alone, but no longer commercially practiced.
Heating of polymer with sulfur

CH2 CH CH CH2 CH2 CH CH CH2

S S
S
S
CH2 CH CH CH2 S
S
CH2 CH CH CH2

Mechanism of curing reaction is not fully understood. Free radical and ionic
intermediates have been suggested.
Today sulfur is used in conjunction with accelerators such as tetramethyl thiuram
disulfide:

H3C S S CH3

N S S N

H3C CH3

Polymers can also be crosslinked with peroxides RO-OR 11

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 Why do we have to know the constitution of polymers?
Architecture:

Linear polymer branched network

Solubility decreases
(mechanical) stability increases

Chemical composition: side groups (homo-or block copolymer), hetero- or

isochain:
Thermal properties, mechanical properties, degradation, solution properties………

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 2.Configuration
Configuration describes those arrangements of atoms that can not be altered
except by breaking bonds.

2.1 Head to tail configuration

Monomers prepared with chain reaction are normally added in a head to tail
configuration.

R
R R R R R R

tail head
Head: part with bigger substituent
1,2-Addition
head-tail
R R R R R R

R R R
R head-head
tail-tail
1,1-Addition
R R R

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 2.2 Configuration involving a carbon-carbon double bond
Polymers from 1,3-dienes can contain four different sequences:

CH2 CH2 CH2 H

C C C C
R H R CH2

cis-1,4 trans-1,4

R
CH2 CH
CH2 C C CH2
CH CH2 R
1,2- 3,4

Polyisoprene:
Isoprene

Natural rubber: all cis-1,4 configuration (Mn~5000, PDI= very high)

Source: Hevea brasiliensis: Bark of tree is cut to release Latex (aqueous dispersion of
rubber with proteins and fatty acids).
Latex is dried on air and bleached

Synthetic natural rubber: prepared with coordination polymerisation or with anionic

polymerisation 14
Polyisoprene is normally vulcanized to become an elastomeric material
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 Polybutadiene-Polystyrene: Styrene-Butadiene Rubber (SBR)

Butadiene

Prepared during WWII due to lack of natural rubber

Radical polymerisation result in a random copolymer:
20% 1,2-configuration, 20% cis-1,4-configuration and 60% trans-1,4 configuration (SBR
is an amorphous polymer)

cis-1,4-polybutadiene
prepared by coordination and anionic polymerisation

Polychloroprene (Neoprene)
Cl

Chloroprene
Prepared by emulsion polymerisation to form almost entirely in the trans-1,4-
configuration
Unusual behaviour of neoprene: can be crosslinked by heat alone
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 2.3 Configuration involving an asymmetric carbon atom

Tacticity: Configuration of repeating unit

isotactic
R H R H R H R H R H R H R H R H

R H H R R H H R R H H R R H H R syndiotactic

R H R H H R R H H R H R R H H R atactic

Isotactic: all stereoisometric centres along the chain are the

same
Syndiotactic: the different chiral centres strictly alternate along the chain
Atactic: random sequence (most polymerisations produce atactic polymers)

Isotactic and syndiotactic polymers are normally prepared with coordination

polymerisation 16

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 Can you think of a way of making regular (syndiotactic or
isotactic) polymers with radical polymerization?

Why do we have to know the configuration of polymers?

A different tacticity or head to head configuration or cis/trans configuration can

affect the polymers in solution such as their solubility. But it affects even more
the behaviour of the polymers in solid state.
A very regular configuration leads to highly organised polymers in the solid
state. Varying configurations act like a defect to the order. Polymers which are
ordered have very different macroscopic properties.

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 3. Conformation

Conformations are arrangements, which are derived from the rotation of atoms
around single bonds

Theoretically, the angle  between the atom A and D can be everything between 0
and 180°.

A
B
C

However, certain conformations (or angles) are preferred, because they are
energetically more stable:

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 gauche trans gauche

The rotation around the single bonds is influenced by:

The size of the substituent
The length of the bonds 19
The environment of the polymer (solution, solid state, temperature)

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 A polymer can posses many conformations: random coil

Sometimes the conformation is more ordered:

helix
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 What problems can arise if we try to react two chain ends
considering that a chain is a random coil?
Do you think the dimension of the coil is affected by temperature
and solvent?

Why do we have to know the conformation of polymers?

Polymers are not rigid rods. They are dynamic systems and can have many
conformations at a time.
A polymer takes up many conformations despite the fact that the all-trans
conformation might have the lowest energy.
Especially when we dissolve a polymer the conformation might have influence on
the solution properties. If a polymer is rather rod-like it might have a different
behaviour in dissolved state than a coil-like polymer.

Rod polymer (all-trans is

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preferred)
Coil like polymer
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 4. Molecular Weight of Polymers

Polymers are polydisperse:

macromolecules do not have the same size, there is a range of sizes (=molecular
mass or number of repeating units)

amount of polymer

molecular weight

Polymers have typically molecular weights between 10000 (10 kDa) and 500000
(500 kDa), but the molecular weight can also reach millions.
The shape of the molecular weight distribution is a result of the polymerisation
process.

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 Why do we have to know the molecular weight of polymers?
All properties of polymers such as solid state and solution properties change with the
molecular weight. It changes dramatically especially at low to medium high molecular
weight

physical property

I II III

Molecular Weight

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 II POLYMERS IN SOLID STATE

1.From a liquid to the solid state

Many monomers are liquids (styrene, methacrylates, acrylates). Polymerisation of

these liquids lead to a more and more viscous solution. Finally, the reaction mixture
cannot be stirred anymore. Why?
The higher the concentration of polymer in a solution or the higher the molecular
weight of the polymer the more chains can entangle. The chains can still slip past
each other but they tend to form entanglements, which can cause a syrup like
behaviour. Finally, we have a solid polymer.

Entanglement

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 However, the structure of a solid polymer does not automatically look like
spaghetti:

Amorphous structure

Interaction between chains (the same interaction as in low molecular weight

compounds) can lead to more complex and ordered structures:

The formation of ordered structures (crystalline structures) in polymers is

dependent on
Constitution
Configuration
The treatment of the polymer (this is important since some polymers might be
able to have a ordered structure but their preparation (experimental conditions)
prevent the formation of higher orders)

Some polymers have strong Intermolecular forces

Dispersion force (van der Waals force)
Dipole Force
Hydrogen bond
These forces can now be responsible that a structure (amorphous or ordered) is
very stable 25

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 2. Crystalline Polymers

Many polymers, including most fibres, are partially crystalline.

The microscopic structure of (partially) crystalline polymers show zones with a
parallel (crystalline) order of polymer chains

Prerequisite for crystallinity: Polymers must be able to organize themselves without

destruction

Amorphous
zone

Crystalline
zone
(crystallite)

This is the fringed micelle model of semi-crystalline

polymers. It is believed now that this model does
not represent the truth!

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 2.1 Crystal structures of polymers

a. Polymers with without side chains

Polyethylene- a polymer with high regularity

Fully extendend zig-zag chain (trans conformation) has the lowest energy and therefore
favoured in polymer crystals

H H H H H H H H H H H H H H H H

orthorhombic

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 Polyamide (and other polycondensates)- regular polymers with strong hydrogen
bonds

Nylon-6 and Nylon-6,6

form sheets

But a asymmetric monomer unit might disturb the order:

H CH3 H
O N N O
O
Can crystallize
O O
n

H H
O O
Cannot crystallize- always amorphous O
N N
OH C
3 28O
n

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 b. Regular polymers- isotactic and syndiotactic chains

Isotactic and syndiotactic polymers can have an

all-trans conformation but can also have an
alternating trans and gauche position.
As a result of alternating trans gauche position
they form helical conformations. These helices
form then (rhombic, tetragonal, hexagonal...)
cells.

Advantage of helix over all-trans conformation:

closer packing

Gaylord, Linear and Stereoregular Addition of

Polymers, Interscience New York, 1959

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 c. Atactic polymers

Atactic polymers are normally totally amorphous. They cannot pack into a close packing

R H R H H R R H H R H R R H H R
H H H H H H H H H H H H H H H H

Exception: If the substituent is small enough, atactic polymers are able to crystallize
Example: Polyvinylalcohol has a crystal structure similar to polyethylene

OH OH OH OH OH

d. Copolymers and branched polymers

Small irregularity do not prevent crystallinity, but with increasing branching density or
branch length and with increasing amount of comonomer the crystallinity is disturbed
and the polymers are amorphous.

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 Which of these polymers might crystallise?

O H
O N
O N
H O O

Polystyrene
a) prepared with coordination polymerisation
b) prepared with radical polymerisation

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