Polymer Chemistry

----
 Development of polymer chemistry

1833: Berzelius, the first use of terminology, polymer

1839: Synthesis of polystyrene
1860s: Poly(ethylene glycol), Poly(ethylene succinate)
1900s: Leo Baekeland, synthesis of phenol formaldehyde resin
1920s: Hermann staudinger
Structure of polymer(long-chain molecules), Novel Prize(1953년)
1939: W.H. Carothers, Nylon synthesis (Du Pont)
1963: Ziegler-Natta, stereoregular polymerization
1974: Paul Flory, polymer solution property
1984: Bruce Merrifield, solid-phase protein process
 Polymers
What is a polymer?
Very Large molecules structures chain-like in nature.
Poly mer
many repeat unit

repeat repeat repeat

unit unit unit
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 7e.
Bulk or Commodity Polymers
Definitions

A. Acoording to the amount of repeating units

monomer : one unit

oligomer : few

polymer : many (poly – many, mer – part)

telechelic polymer : polymer containing reactive end group

(tele = far, chele = claw)

telechelic oligomer : oligomer containing reactive end group

macromer(=macro monomer) : monomer containing long chain

Definitions
B. DP : Degree of polymerization

The total number of repeating units

contained terminal group

C. The kinds of applied monomers

One kind : Homopolymer

Two kinds : Copolymer
Three kinds : Terpolymer
D. Types of copolymer

Homopolymer : -A-A-A-A-A-A-A-A-

Random copolymer : -A-B-B-A-B-A-A-B-

Alternating copolymer : -A-B-A-B-A-B-A-B-

Block copolymer : -A-A-A-A-B-B-B-B-

Graft copolymer : -A-A-A-A-A-A-A-A-

B-B-B-B-B-
Representation of polymer types

(a) linear (b) branch

(c) network
Representation of polymer architectures

(a) star polymer (b) comb polymer

(d) semi- ladder

(c)ladder polymer
(or stepladder) polymer
Representation of polymer architectures

(e) polyrotaxane (f) polycatenane

(g) dendrimer
 Range of Polymers
• Traditionally, the industry has produced two
main types of synthetic polymer – plastics and
rubbers.
• Plastics are (generally) rigid materials at
service temperatures
• Rubbers are flexible, low modulus materials
which exhibit long-range elasticity.
Range of Polymers
 Range of Polymers
• Another way of classifying polymers is in
terms of their form or function
Polymerization Processes

A. Classification of polymers to be suggested by Carothers

Addition polymers : repeating units and monomers are same

Condensation polymers : repeating units and monomers are not equal,

to be split out small molecule
 Types of Polymerization
• Chain-growth polymers, also known as
addition polymers, are made by chain
reactions
 Types of Polymerization
• Step-growth polymers, also called
condensation polymers, are made by
combining two molecules by removing a small
molecule
Other examples

1. Polyester from lactone &

from ω-hydroxycarboxylic acid

O O

O C O R C

OH R CO2H O R C + H2O
 Other examples

2. Polyamide from lactam and

from ω-aminocarboxylic acid

O O
NH C NH R C
R

O
+ H2O
H2N R CO2H NH R C
 Other examples

3. Polyurethane from diisocyanate and dialcohol

and from diamine and bischloroformate:

OCN R NCO + HO R' OH

O O

CNH R NHCO R' O

O O

H2N R NH2 + ClCO R' OCCl

O O

CNH R NHCO R' O + 2HCl

 Other examples

4. Hydrocarbon polymer from ethylene (1.13), and from α,ω-dibromide

initiator
CH2 CH2 CH2CH2

2Na
BrCH2(CH2)8CH2Br CH2CH2 + 2NaBr
5
 Polymerization Processes
B. Modern classification of polymerization according to
polymerization mechanism

Step growth polymerization: Polymers build up stepwise

Chain growth polymerization: Addition polymerization molecular weights increase

successively, one by one monomer

Ring-opening polymerization may be either step or chain reaction

Step-reaction Polymerization

A. Monomer to have difunctional group

1. One having both reactive functional groups in one molecule

A R B R X

HO R CO2H O R C + H2O

O
+ H2O
H2N R CO2H NH R C
2. Other having two difunctional monomers

A R A + B R' B R X R' X

OCN R NCO + HO R' OH

O O

CNH R NHCO R' O

O O

H2N R NH2 + ClCO R' OCCl

O O

CNH R NHCO R' O + 2HCl

 B. Reaction : Condensation reaction using functional group

Example - Polyesterification

n HO CO2H O C + nH2O
n

nHO2C CO2H + nHOCH2CH2OH

O O

C COCH2CH2O n
+ 2nH2O
C. Carothers equation

( NO : number of molecules
N : total molecules after a given reaction period.
NO – N : The amount reacted
P : The reaction conversion )

NO N
P= Or N = NO(1 P)
NO

( DP is the average number of repeating units of all molecules present)

DP = NO/N

1
DP =
1-P

For example 1
DP =
At 98% conversion 1- 0.98
 (A) Unreacted monomer

A A A A A A A A A A A A
(a)
B B B B B B B B B B B B

(B) 50% reacted, DP = 1.3

A A A A A A A A A A A A
(b)
B B B B B B B B B B B B

(C) 75% reacted, DP = 1.7

A A A A A A A A A A A A
(c)
B B B B B B B B B B B B

(D) 100% reacted, DP = 3

A A A A A A A A A A A A
(d)
B B B B B B B B B B B B
 Chain-reaction Polymerization

A. Monomer : vinyl monomer

χCH2=CH2

B. Reaction : Addition reaction initiated by active species

C. Mechanism :

Initiation
.
R + CH2=CH2 → RCH2CH2 .
Propagation
.
RCH2CH2 + CH2=CH2 → RCH2CH2CH2CH2 .
 Comparison of Step-Reaction and Chain-Reaction Polymerization

Step Reaction Chain Reaction

Growth occurs throughout matrix by Growth occurs by successive addition of

monomer units to limited number of
reaction between monomers, oligomers,
growing chains
and polymers
DP can be very high
DPa low to moderate
Monomer consumed relatively slowly, but
Monomer consumed rapidly while
molecular weight increases rapidly
molecular weight increases slowly
Initiation and propagation mechanisms different
No initiator needed; same reaction Usually chain-terminating step involved
mechanism throughout Polymerizaion rate increases initially as
No termination step; end groups still reactive initiator units generated; remains relatively
Polymerization rate decreases steadily as constant until monomer depleted
functional groups consumed
aDP, average degree of polymerization.
 Nomenclature

A. Types of Nomenclature

a. Source name : to be based on names of corresponding monomer

Polyethylene, Poly(vinyl chloride), Poly(ethylene oxide)

b. IUPAC name : systematic name

Poly(methylene), Poly(1-chloroethylene), Poly(oxyethylene)

c. Functional group name :

Acoording to name of functional group in the polymer backbone

Polyamide, Polyester
 1.7 Nomenclature

d. Trade name : The commercial names by manufacturer Teflon, Nylon

e. Abbreviation name : PVC, PET

f. Complex and Network polymer : Phenol-formaldehyde polymer

g. Vinyl polymer : Polyolefin

Vinyl polymers

A. Vinyl polymers
a. Source name : Polystyrene, Poly(acrylic acid),
Poly(α-methyl styrene), Poly(1-pentene)
b. IUPAC name : Poly(1-phenylethylene), Poly(1-carboxylatoethylene)
Poly(1-methyl-1-phenylethylene), Poly(1-propylethylene)
Polystyrene Poly(acrylic acid)

CH 2CH CH2CH
CO2H

Poly(α-methylstyrene) Poly(1-pentene)
CH3
CH2C
CH2CH
CH2CH2CH3
 Vinyl polymers

B. Diene monomers

CH 2CH CH2CH CHCH 2

HC CH 2

1,2-addition 1,4-addition

Source name : 1,2-Poly(1,3-butadiene) 1,4-Poly(1,3-butadiene)

IUPAC name : Poly(1-vinylethylene) Poly(1-butene-1,4-diyl)

Nonvinyl Polymers

O CCH2CH2

oxy 1-oxopropane-1,3-diyl

O CH2CH2 O C C

oxy ethylene oxy terephthaloyl

 * Representative Nomenclature of Nonvinyl Polymers

Monomer Polymer Source or IUPAC name

structure repeating unit Common Name

O
CH2CH2O Poly(ethylene oxide) Poly(oxyethylene)
H2C CH2

HOCH2CH2OH CH2CH2O Poly(ethylene glycol) Poly(oxyethylene)

O O

H2N(CH2)6NH2 NH(CH2)6NHC(CH2)8C

HO2C(CH2)8CO2H Poly(hexamethylene Poly(iminohexane-

sebacamide) or Nylon6,10 1,6-diyliminosebacoyl)
 Nonvinyl copolymers

a. Poly(ethylene terephthalate-co-ethylene isophthalate)

O O O
OCH2CH2O C C OCH2CH2OC

C
O

b. Poly[(6-aminohexanoic acid)-co-(11-aminoundecanoic acid)]

O O

NH CH2 C NH CH2 C
5 10
 Thermodynamics
• Thermodynamics of polymerization
determines the position of the equilibrium
between polymer and monomer(s).
• The well known thermodynamic expression:
G = H - TS
yields the basis for understanding
polymerization/depolymerization behavior.
 Thermodynamics
• For polymerization to occur (i.e., to be
thermodynamically feasible), the Gibbs free
energy of polymerization Gp < 0.
• Standard enthalpy and entropy changes, Hop
and Sop are reported for reactants and
products in their appropriate standard states.
Generally:
– Temperature = 25oC = 298K
– Monomer – pure, bulk monomer or 1 M
solution
– Polymer – solid amorphous or slightly
crystalline
 Thermodynamics
• Polymerization is an association reaction such
that many monomers associate to form the
polymer

• Thus: Sp < 0 for nearly all polymerization

processes
 Thermodynamics
• Since depolymerization is almost always
entropically favored, the Hp must then be
sufficiently negative to compensate for the
unfavorable entropic term.

• Only then will polymerization be

thermodynamically favored by the resulting
negative Gp.
 Thermodynamics
In practice:
– Polymerization is favored at low
temperatures: TSp is small

– Depolymerization is favored at high

temperatures: TSp is large
 Thermodynamics
• Therefore, thermal instability of polymers
results when TSp overrides Hp and thus Gp
> O; this causes the system to spontaneously
depolymerize (if kinetic pathway exists).
 Thermodynamics
• the activation energy for the depropagation
reaction is higher,
• Compared to the propagation reaction its rate
increases more with increasing temperature
• As shown below, this results in a ceiling
temperature.
 Thermodynamics
• ceiling temperature
– the temperature at which the propagation and
depropagation reaction rates are exactly equal at
a given monomer concentration
6

5
kdp
4
-1

3
k, sec

kp[M]
2
kp[M] - kdp
1
Tc
0
300 350 400 450 500 550 600
o
Temperature, K
 Thermodynamics
• At long chain lengths, the chain propagation
reaction
kp
Pn* + M *
Pn+1
kdp

• is characterized by the following equilibrium

expression:
kp [  Pn*1 ] 1
 
k dp [  Pn ][M] [ M ]c
*
 Thermodynamics
• At [M]c = [M]o, Tc = Hpo/Spo
Specific Examples of Monomer - Polymer Equilibrium

kcal/mol cal/mol-deg (H/S)

Monomer Hp Sp Tc(oC)
Ethylene -21.2 -24 610
Isobutylene -12.9 -28 175
Styrene -16.7 -25.0 395
-methyl styrene -8.4 -24 66
2,4,6-trimethyl styrene -16.7 --- ---
TFE -37 -26.8 1100
 Thermodynamics
• Notice the large variation in the -H values.
• ethylene > isobutylene - attributed to steric hinderance
along the polymer chain, which decreases the
exothermicity of the polymerization reaction.

• ethylene > styrene > -metylstyrene - also due to

increasing steric hinderance along the polymer chain.

• Note, however, that 2,4,6-trimethylstyrene has the same -

H value as styrene. Clearly, the major effect occurs for
substituents directly attached to the polymer backbone.
 Synthetic Polymer
Introduction
• A polymer is a large molecule composed of
many smaller repeating units.
• First synthetic polymers:
– Poly(vinyl chloride) in 1838
– Polystyrene in 1839
• Now, 250 billion pounds produced annually,
worldwide.

50
 Classes of Polymers
• Addition, or chain-growth, polymers

• Condensation, or step-growth, polymers

=>
51
 Addition Polymers
• Three kinds of intermediates:
– Free radicals
– Carbocations
– Carbanions
• Examples of addition polymers:
– polypropylene plastics
– polystyrene foam insulation
– poly(acrylonitrile) Orlon® fiber
– poly(methyl -methacrylate) Plexiglas ®
=>

52
 Free Radical
Polymerization

=>
53
 Chain Branching
• Low-density polyethylene:
– soft and flimsy
– highly branched, amorphous structure

=>

Chapter 26 54
 Cationic Polymerization
• Alkene is treated with an acid.
• Intermediate must be a stable carbocation.

Chapter 26 => 55
 Good Monomers for
Cationic Polymerization

=>

56
 Anionic Polymerization
• Alkene must have an electron-withdrawing
group like C=O, CN, or NO2.
• Initiator: Grignard or organolithium reagent.

=>

Chapter 26 57
Stereochemistry

=>
58
 Properties of Polymers
• Isotactic and syndiotactic polymers are
stronger and stiffer due to their regular
packing arrangement.
• Anionic intermediate usually gives isotactic or
syndiotactic polymers.
• Free radical polymerization is nearly random,
giving branched atactic polymers.
=>

59
 Ziegler-Natta Catalyst

• Polymerization (for terminal alkene) is

completely stereospecific.
• Either isotactic or syndiotactic, depending on
catalyst.
• Polymer is linear, not branched.
• Example of catalyst: solution of TiCl4 mixed
with solution of (CH3CH2)3Al and heated for an
hour.
=>
60
 Vulcanization
• Discovered accidentally
by Goodyear, dropped
rubber and sulfur on a
hot stove.
• Sulfur produces cross-
linking, strengthening the
rubber.
• Hardness can be
controlled by varying the
amount of sulfur.
=>

61
 Synthetic Rubber
• With a Ziegler-Natta catalyst, a polymer of
1,3-butadiene can be produced, in which all
the additions are 1,4 and the remaining
double bonds are all cis.
• It may also be vulcanized.

=>
Chapter 26 62
 Condensation Polymers
• Polymer formed by ester or amide linkages
between difunctional molecules.
• Step growth: Monomers do not have to add one at
a time. Small chains may condense into larger
chains.
• Common types:
– Polyamides
– Polyesters
– Polycarbonates
– Polyurethanes =>
63
 Polyamides: Nylon
Usually made from reaction of diacids with
diamines, but may also be made from a
single monomer with an amino group at one
end and acid group at other.

=>

Chapter 26 64
 Polyesters
• Dacron® and Mylar®: polymer of
terephthalic acid and ethylene glycol.
• Made by the transesterification of the
methyl ester.

=>

65
 Polycarbonates
• Esters of carbonic acid.
• Carbonic acid is in equilibrium with CO2 and
water, but esters are stable.
• React phosgene with bisphenol A to obtain
Lexan® for bulletproof windows.

=>

Chapter 26 66
 Polyurethanes
• Esters of carbamic acid, R-NH-COOH.
• Urethanes are prepared by reacting an
alcohol with isocyanate.
• Polyurethanes are prepared by reacting a
diol with a diisocyanate.

=>

Chapter 26 67
 Polymer Crystallinity
• Microscopic crystalline regions.
• A linear polymer will have a high degree of
crystallinity, and be stronger, denser and
more rigid.

=>

Chapter 26 68
 Thermal Properties
• Glasses at low temperature, fracture on
impact.
• At the glass transition temperature, Tg,
crystalline polymers become flexible.
• At the crystalline melting temperature, Tm,
crystalline polymers become a viscous liquid,
can be extruded to form fibers.
=>

69
 Crystalline vs. Amorphous
Phase transitions for long-chain polymers.

=>

70
 Plasticizers

• Nonvolatile liquid that dissolves, lowers the

attraction between chains, and makes the
polymer more flexible.
• Example: Dibutyl phthalate is added to
poly(vinyl chloride) to make it less brittle.
The plasticizer evaporates slowly, so “vinyl”
becomes hard and inflexible over time.
=>

71
Natural Polymers
 What is a Natural Polymer?
• The natural polymer group includes naturally occurring
polymers and chemical modifications of these polymers.
• This group includes:
– Cellulose (main structural component of plants)
– Starch
– Lignin
– Chitin
– RNA & DNA
– And various other polysaccharides (sugars)
 Everyday Uses
• Natural polymers are not so much used, but rather are
found in nature.
• The group includes proteins, RNA & DNA,
polysaccharides, amino acids, etc.
• But, they are in fact used in a different sense; Natural
polymers are being used all the time without knowing it,
as all living organisms rely on them to survive.
 RNA & DNA
• RNA and DNA contain sugar units, making them
polysaccharides, but they have well ordered groups
attached to the sugars giving them unique capabilities.
• Messenger RNA are an example of natural polymers.
• These are what make possible proteins, peptides,
enzymes.
– Enzymes consists of the chemistry inside living organisms
– Peptides consists of some of the more interesting structural
components of skin, hair, etc.
 Amino Acids
• Amino acids are structurally bifunctional.
• Today, there are 20 known/identified amino
acids.
• They are formed when a carboxylic group
(COOH) and an amine group (NH2) react
through the loss of water. This creates an
amide.
 Naming
• When you name an amino acid, the carbon in the carboxylic acid group is
numbered as 1. Identify your longest parent-chain of carbons with the
carboxylic acid group.
• Add “amino” before your prefix, and “oic acid” after your prefix.
• Indicate the placement of the NH2 group by adding the number in front of
your “amino”.
• If there is an attachment, such as methyl (CH3), then in the name you identify
it AFTER the “amino”.
– Ex: 2-amino-4-methylheptanoic acid
 Example

• 2-aminopropanoic acid
 Proteins
• Proteins are the basic strutural
material of plants and animals.
• There are over 10 billion different
proteins, all constructed from the 20
known amino acids.
• The repetoire of an amide bond forms
a protein.
• The number of amino acids in a
protein can range from two to several
thousands.
 Polypeptides
• Polypeptides are made of chains of amino
acids. A protein is made of polypeptide
molecules.
• Polypeptides also contributes towards silk,
keratin and hair.
 Natural Rubber
• Natural rubber is another example of a natural
polymer.
• It is made from only Carbon and Hydrogen.
 Natural Rubber
• Soft and sticky, obtained from rubber tree.
• Long chains can be stretched, but then return
to original structure.
• Chains slide past each other and can be pulled
apart easily.
• Structure is cis-1,4-polyisoprene.

=>
n
84
 Properties
• The wide range of properties and applications
vary depending on which natural polymer
you’re looking at.
• Natural polymers tend to be readily
biodegradable.
• Their rate of degredation is generally inversely
proportional to the extent of chemical
modification.
• They can be extracted from nature.
Thermoplastics
 Structure–Property Relationships in
Thermoplastics

 Branched polymer - Any polymer consisting of chains that

consist of a main chain and secondary chains that branch off
from the main chain.
 Crystallinity is important in polymers since it affects
mechanical and optical properties.
 Tacticity - Describes the location in the polymer chain of
atoms or atom groups in nonsymmetrical monomers.
 Liquid-crystalline polymers - Exceptionally stiff polymer
chains that act as rigid rods, even above their melting point.
Head-to-tail versus head-to-head arrangement of repeat units. The head-to-tail
arrangement is most typical.
Copolymerization
produces the polymer
ABS which is really
made up of two
copolymers, SAN and
BS, grafted together.
 Effect of Temperature on Thermoplastics

 Degradation temperature - The temperature above which a

polymer burns, chars, or decomposes.
 Glass temperature - The temperature range below which the
amorphous polymer assumes a rigid glassy structure.
The effect of
temperature on
the structure
and behavior of
thermoplastics.
The effect of
temperature on
the modulus of
elasticity for an
amorphous
thermoplastic.
Note that Tg and
Tm are not fixed.
The relationship between
the density and the
temperature of the
polymer shows the
melting and glass
temperatures. Note that
Tg and Tm are not fixed;
rather, they are ranges of
temperatures.
 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.

The folded chain, model for crystallinity in polymers,

shown in (a) two dimensions and (b) three dimensions.
 Mechanical Properties of Thermoplastics

 Viscoelasticity - The deformation of a material by elastic

deformation and viscous flow of the material when stress is
applied.
 Relaxation time - A property of a polymer that is related to
the rate at which stress relaxation occurs.
The stress-strain curve for 6,6-nylon, a typical thermoplastic polymer.
 Elastomers (Rubbers)

 Geometric isomer - A molecule that has the

same composition as, but a structure different
from, a second molecule.
 Diene - A group of monomers that contain two
double-covalent bonds. These monomers are
often used in producing elastomers.
 Cross-linking - Attaching chains of polymers
together to produce a three-dimensional
network polymer.
 Vulcanization - Cross-linking elastomer chains
by introducing sulfur or other chemicals.
The cis and trans structures of isoprene. The cis form is useful for
producing the isoprene elastomer.
(a) When the elastomer contains no cross-links, the application of a force
causes both elastic and plastic deformation; after the load is removed, the
elastomer is permanently deformed. (b) When cross-linking occurs, the
elastomer still may undergo large elastic deformation; however, when the
load is removed, the elastomer returns to its original shape.
Cross-linking of polyisoprene chains may occur introducing strands of
sulfur atoms. Sites for attachment of the sulfur strands occur by
rearrangement or loss of a hydrogen atom and the breaking of an
unsaturated bond.
The stress-strain curve for an elastomer. Virtually all of the deformation
is elastic; therefore, the modulus of elasticity varies as the strain changes.
 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.

The structure of the styrene-butadiene (SB) copolymer in a thermoplastic

elastomer. The glassy nature of the styrene domains provides elastic behavior
without cross-linking of the butadiene.
 Thermosetting Polymers

 Phenolics
 Amines
 Urethanes
 Polyesters
 Epoxies
 Polyimides
 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.

Structure of a phenolic. In (a) two phenol rings are joined by a condensation

reaction through a formaldehyde molecule. Eventually, a linear chain forms. In
(b), excess formaldehyde serves as the cross-linking agent, producing a network,
thermosetting polymer.
 Polyester Chemistry
• Unsaturated Polyesters
– Thermoset reaction between a difunctional acid (or anhydride)
and a difunctional alcohol (glycol)

O O
C6H4(COOH)2 + (CH2)2(OH)2 -[(CH2)2 -O- C - C-O]-
terphthalic acid + ethylene glycol Polyethylene terephthalate
(PET)

– Acids include: maleic, fumaric, isophthalic, terphthalic, adipic, etc.

– Anhydrides include: maleic, phthalic
– Glycols include ethylene glycol, diethylene glycol, propylene glycol

117
 Michael addition of divinyl monomer with amine

Poly(amido amine) synthesis via (a) primary and (b) secondary amines.
 Epoxy Systems

Network
 Epoxy Systems

• Advantageous Properties of epoxies

– High chemical and solvent resistance
– Outstanding adhesion to many substrates
– Good impact resistance
– Good electrical properties
Epoxy Systems
PMD: Pyromellitic dianhydride

ODA: Oxydianiline
 Adhesives

 Chemically Reactive Adhesives

 Evaporation or Diffusion Adhesives
 Hot-Melt Adhesives
 Pressure-Sensitive Adhesives
 Conductive Adhesives
 Additives for Plastics

 Fillers
 Pigments
 Stabilizers
 Antistatic Agents
 Flame Retardants
 Plasticizers
 Reinforcements
 Catalysts