1.

3
Basic Terms and Concepts in Polymer Chemistry

History of Macromolecular Chemistry

1922
1953
1963
1974

Definition of the term polymer by Hermann Staudinger

Nobel Prize for Hermann Staudinger (concept)
Nobel Prize for Karl Ziegler and Giulio Natta (olefin polymerization)
Nobel Prize for Paul J. Flory (polymers in solution)

1901
1928
1930
1934
1937
1939
1945
1946
1952
1954

Polyacrylates (Rhm Chemie)

Plexiglass (Rhm Chemie)
Polystyrol, Polyacrylonitrile (BASF)
Polyvinylchloride (BASF)
Polyamides (DuPont, BASF), Polyurethanes, Polybutadiene (IG Farben)
Polyethylene, LDPE (ICI)
Poly(ethylene terephthalate) (ICI)
Teflon (DuPont)
Polyethylene, HDPE (Ziegler)
Polypropylene (Natta)
Mhlhaupt, Angew. Chem. Int. Ed. 2004, 43, 1054.

Polymer Chemistry

51

Denition of a Polymer

Denition of a polymer according to Hermann Staudinger:

property

A polymer is a large molecule constituted from (identical) smaller structural repeating units with a
length sucient such that molecules with n and n+1 repeating units are in

4
8
12
number of repeating units

16

If properties are indistinguishable, polymers are also inseparable; polymers are polydisperse!
Polymer Chemistry

Staudinger, Helv. Chim. Acta 1922, 5, 785.

52

Polymer Types, Architectures, Microstructures

Homopolymers: one type of repeating units (but dierent architectures)

linear

star

branched

hyperbranched

network

Copolymers: dierent types of repeating units (and microstructures)

random

AB diblock

ABC triblock

segmented

graft

alternating

ABA triblock

miktoarm star

tapered

brush

Polymer Chemistry

53

Molecular Weight (MW) and Molecular Weight Distribution (MWD)

Polymers do not have dened molar masses but molecular weight distributions (MWD)
Dierent molecular weight averages, width, and shape
Molecular weight averages are moments of the molecular weight distribution
number average molecular weight

Mn =

ni Mi
ni

weight average molecular weight

Mp M

Mw

Mz

Mw =

n i M i2
ni Mi

centrifuge average molecular weight

molecular weight distribution

n i M i2

z+1 average molecular weight

log MW
Polymer Science

Mz =

n i M i3

M z+1 =

n i M i4
n i M i3
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Molecular Weight Averages and Polydispersity Index

Mn =

ni M i
8 5000
= 5000
=
ni
8

Mw =

n i M i2
8 50002
= 5000
=
ni M i
8 5000

Mw
PDI =
=1
Mn
Mn =

ni M i
4 9000 + 4 1000
= 5000
=
ni
4+4

Mw =

n i M i2
4 90002 + 4 10002
= 8200
=
ni M i
4 9000 + 4 1000

PDI =

Polymer Chemistry

monodisperse (molecularly uniform)

Mw
= 1 .64
Mn

polydisperse

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Thermal Transitions of Polymers

melting transition
Tm

polymer melt

highly crystalline

glass transition
Tg

amorphous, glassy
partially crystalline

Polymer Science

56

Thermal Transitions of Polymers

Analysis of thermal transitions with Dierential Scanning Calorimetry (DSC)

crystalline polymer

partially crystalline polymer

Tm

Tm

melting

melting
Tg
Tg

slow

amorphous polymer

crystallization
Tm

enthalpy

enthalpy

crystallization

melting

Tg

Tg

Tg

Tg

crystallization
crystallization

fast
temperature

Polymer Science

temperature

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Mechanical Properties of Polymers

exible polymers (T < r.t.)

g

viscous liquid

thermoplastic elastomer

elastomer

rigid polymer chains (T > r.t.)

g

fiber axis

amorphous thermoplast

Polymer Science

crystalline thermoplast

duromer

ber

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Determination of Mechanical Properties of Polymers by Tensile Testing

stress

ber

thermoplast

elastomer

strain

Youngs modulus E (slope in the elastic deformation region) is a measure for stiness
Energy at break (area under stress-strain curve) is a measure for toughness
Yield stress (maximum at the end of the elastic deformation region) is a measure for strength
Polymer Science

59

Step-Growth Reactions

Polycondensations
n

O
OH

HO

n HO

n H2O

O
O

ethylene glycol
BB monomer

terepththalic acid
AA monomer

O
NH2

HO

N
H

n H2O

6-aminohexanoic acid
AB monomer

n O

N
N

bisphenol A
AA monomer
Polymer Chemistry

Nylon-6

Polyadditions
OH

poly(ethylene terepththalate) (PET)

HO

OH

OH

toluene diisocyanate (TDI)

BB monomer

H
N

O
O

H
N

O
O

linear poly(urethane)

N
n

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Origin of Polydispersity and MW Limitations in Step Growth Reactions

B
A
6 A

AB

B
AB

AB
B

AB

M n = 2 .0
M w = 2 .4

PDI = 1.2
conversion = 50%

Polymer chain growth is a statistical process

Conversion limits molecular weight
Polymer Chemistry

61

Chain Polymerizations

Example: Radical polymerization

initiator decomposition

NC

CN

initiation

N2

CN

OMe
CN

CN

O O
n

propagation (chain growth)

O
CN

OMe
CN

Initiator decomposition and initiation are statistical processes, but not responsible for molecular
weight distribution and limitation

Polymer Chemistry

62

Chain Termination and Transfer Reactions in Radical Chain Polymerizations

Example: Radical polymerization

combination
CN

O O
n

O O

O O

CN

CN

termination

O O
n

O O

O O

CN

O
n

H
H

disproportionation
CN

O O
n

+
O O

O O

CN

O
n

CN

termination

O O
n

O O

CN

O
n

transfer
CN

O O
n

CN

O O
n

+ H

Termination and transfer reactions are statistical processes that cause molecular weight
distribution and limit molecular weight

Polymer Chemistry

63

Living Chain Polymerizations

Example: anionic polymerization

Li

initiation

Li
CH

CH

Li

propagation (chain growth)

Li

n
CH

CH

n
Li

quenching

CH

H
Li

CH2

OH

Initiation is fast (but not ininitely fast), termination and transfer reactions are absent, growth
is not a statistical processes; narrow MWD and controlled MW

Polymer Chemistry

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Summary of the Polymerization Mechanisms

Step Growth

conversion

degree of polymeriztation Pn

Carothers equation
1
=
1

degree of polymeriztation Pn
1

Living

induction
period

gel
effect

kinetic control

glass
effect

conversion

SchulzFlory distribution

weight fraction

weight fraction

weight fraction
Polymer Chemistry

conversion

0
log MW

Poisson distribution

SchulzFlory distribution

conversion and initiator control

degree of polymeriztation Pn

Chain Growth

0
0

log MW

log MW
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Summary of the Polymerization Mechanisms

Step Growth

conversion

degree of polymeriztation Pn

PDI = 1 + conv

0
Polymer Chemistry

conversion

polydispersity index PDI

induction
period

gel
effect

kinetic control

glass
effect

conversion

induction
period

gel and glass

effect

conversion

conversion and initiator control

degree of polymeriztation Pn

Carothers equation
1
=
1

degree of polymeriztation Pn
polydispersity index PDI

Living

polydispersity index PDI

Chain Growth

conversion

2
=1+

conversion

1
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Applications of Polymers
Thermal Insulation Materials

Packaging Materials

Structural Materials

Optical Fibers and Components

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