SYNTHETIC ORGANIC

POLYMERS

Convenor: Dr. Fawaz Aldabbagh

Polymers are large molecules made up of repeating units called Monomers

The synthetic process is Polymerization.
E.g.
Polymerization

H2C CH2

CH2 CH2

Monomer

Polymer

O
Monomer

Polymerization

CH2 CH2 O

Polymer

Note define repeating unit in terms of monomer structure

Degree of Polymerization is the number of monomer units in a Polymer
However, for synthetic polymers it is more accurate to state average degree of
polymerization (DP
)

A polymer prepared from a single monomer is a homopolymer

If two or more monomers are employed, the product is a copolymer

Linear polymer has no branching

Graft copolymer is an example of a branched network

Two main classifications of Polymerization

Addition reaction or Chain growth
Molecular weight increases by successively adding monomers to a reactive polymer
chain end resulting in high molecular weights at low conversions.

STEP reaction or growth

Polymers are formed by linking monomer molecules to form dimers, trimers and
higher species in a step-wise fashion. The most abundant species react, and thus
high molecular weight formed only beyond 99% conversion.

Polymerization Conversion (p)

P =

M0 - Mt
M0

M0 = initial number of monomer molecules

Mt = Number of monomer molecules at time t

Ionic Chain (addition)-Growth Polymerization

The choice of ionic procedure depends greatly on the electronic
nature of the monomers to be polymerized

Vinyl monomers with electron-withdrawing groups

CN
CN

CO2R

CO2R

CO2R

Anionic Polymerization
Vinyl monomers with electron-donating groups
N
OR

SR

Cationic Polymerization
Monomers and reagents should be scrupulously purified; water and oxygen
should be removed.
Polymerizations carried out at very low temperatures

Anionic Polymerizations
Initiators include alkyl lithiums and sodium amide

Cationic Polymerization

-- the formed carbocation must be quite stable

+
Stable tertiary carbocation

H+

OR
H+

+
OR
stable oxonium ion

E.g. proton initiates polymerization of isobutane (2-methylpropene)

BF3/H2O
n
Adhesive, sealant, insulating oil, lubricating oil

Reactions of water with reactive carbanions and carbocations

CN

CN

acid

CN

CN

CN

CN

n
+

OH

Note viable substrates for anionic polymerizations do not have -protons

H
H

H
base

H
+

OMe

OMe

OMe

OMe

OMe

H3O+

OMe

Chain Reaction: Free Radical Polymerization

RO

Initiation

2 RO

OR

RO

RO

Ph

Propagation

Ph

RO

RO
Ph
Ph

Random Termination

n
Ph

Ph

Dead chains

Conventional Radical Polymerization

Advantages
1/wide range of vinyl monomers polymerizable
2/can be carried out in bulk, water, organic solvents and other solvents

3/no rigorous purification or drying of reagents required

Conditions: Usually heat required for initiation
Initiator decomposition time should be considered

- Amount of initiator, reaction temperature and initiator half-life (slow decomposition)

Initiation Rate = Termination Rate - steady state kinetics apply

Overall,
[radical concentration] = low
Since termination (disproportionation and coupling mechanism) is random, a broad
MWD results. This polymer is dead (cannot initiate new monomer additions).

Examples of Polymers Prepared by Radical Polymerization

Monomer

Polymer

CH2CH

Poly(styrene)

CH2CH

CN

n
CH2CH

Poly(acrylonitrile)

CN

O
MeO

Poly(methylacrylate)

OMe
H

n
H

O
Me

CH2CH

O
O

C
Me

Poly(vinylacetate)

Advantages of Radical Polymerization

1. Wide variety of vinyl monomers can be polymerized (electron rich and
deficient DBs)

2. Can be carried out in bulk and in a wide variety of solvents, which include
water and organic solvents
3. No rigorous purification of reagents or drying of solvents required
4. Rapid formation of high molecular weight polymer after small conversions of
monomer to polymer ( chain (addition) polymerization)
5. Living/controlled polymerizations enable easy formation of block copolymers
and sophisticated architectures

75% of commercial polymers are made by radical polymerizations

Some monomers can only be polymerized by radical means, e.g. acrylic acid (AA)
H

AIBN
C

C
O

OH

n
COOH

Ion-exchange resins, smart polymers

Radical Polarity
Polar Effects are important in radical polymerizations, and can give
alternating copolymers

CN
R

Ph

Ph

Ph

CN

R
n

Ph

CN

Ph

CN

Chain Reaction initiation, propagation, termination

Chain polymerization with termination
e.g. conventional radical polymerization
Life time of polymer radical chain is about 1 second
Initiator added so to slowly decompose throughout
polymerization time
Typically, rate of initiation = rate of termination
Therefore, [propagating radical] remains constant
Steady State

DP

100
50
conversion

Chain polymerization without termination

e.g. nitroxide-mediated radical polymerization
(NMP)

DP =

DP

Living

[monomer]
[Initiator]

Initiator decomposes quickly, and polymer chains have long life times

100
50
conversion

Nitroxide-mediated Controlled/living Radical Polymerization (NMP)

propagation

T = Nitroxide
P = Propagating radical

T is sterically congested
Features:
1. Molecular weight increases linearly with conversion
2. Narrow molecular weight distributions obtained
3. Polymer chains contain living ends enabling chain extension or block
copolymer synthesis
Block copolymer synthesis
AAAA

AAAA

propagation

Bn
AAAA

BBBB

B
n

Conventional Radical Polymerization

Broad MWD

Dead Polymer

Controlled Radical Polymerization

T
T
T
T

Narrow MWD

Living Polymer

Life time of radicals extended from 1 second to hours, as the radicals

do not get involved in irreversible bimolecular termination reactions,
since radicals are trapped by nitroxide reversibly
Initiator must decompose quickly to insure narrow MWD

Example of Block Copolymer Formation

n-1
Ph
Ph

m
O

OMe

D : n = 60
: m = 20

AIBN, heat
SG1

Ph
n

n = 60
Ph

First living poly(styrene) block

heated in the presence of methyl
acrylate to give diblock D

O OEt

n-1
Ph

Please correct block copolymer structure in questions

Reversible trapping added to

propagation
to
prevent
irreversible termination

OEt

heat

Ph

n-1
Ph

N
O

OEt
P
OEt
O

SG1

propagation

OMe

m = 20

n-1
Ph
Ph

O N
m
O

OMe

D : n = 60
: m = 20

O
P

O
O

Me

H
C

C
MeO

Me

n
O

CH2 C
C

AIBN

Poly(methyl methacrylate)

OMe

perspex

MMA

Nitroxides cannot control MMA Polymerizations

H

CH3

CO2 Me

PMMA

N
O

OEt
P
OEt
O

SG1
H

disproportionation

CH2
C

H
PMMA=

+
CO2 Me

OEt
N
P
OEt
OH O
SG1-H

McHale, Aldabbagh, Zetterlund, J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 2194-2203

Alternating, Block and Graft Copolymers are made by radical copolymerization

AIBN, heat
excess small
monomer

macromonomer

Graft Copolymer

Graft Copolymer Formation

Recent Example of a Graft Copolymer Synthesis

Copolymerization

macromonomer

monomer

Poly(AA)

Graft copolymer

NIPAM
H

Br

CH2 C

CH2 C

C
OH

C
CH C
n 2
C

C
OH

H2C

+
OCH2CH3

Poly(acrylic acid) macromonomer

CH

H3C

CH N
H3C

N-Isopropylacrylamide
NIPAM monomer (excess)

Insoluble in water above the lower critical solution temperature (LCST)

McHale, Aldabbagh, Carroll, Yamada, J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 4394-4400

Copolymerization of Poly(AA) Macromonomer with NIPAM in ethanol at 60 C

0.6

W (log M )

0.5

macromonomer

4%

0.4
0.3

63%
40%

19%

0.2
0.1
0.0
2

log M

Shift to higher MW

Dual-Responsive Smart Graft Copolymer

Copolymerization

macromonomer

Poly(AA)

Insoluble in water

Monomer

Graft copolymer

NIPAM

Soluble in NaOH (aq)

Poly(NIPAM)
in water
(40C)

Graft copolymer
in NaOH solution
(40C)

Graft copolymer
in NaOH (50C)

McHale, Aldabbagh, Carroll, Yamada, J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 4394-4400
Gibbons, Carroll, Aldabbagh, Yamada, J. Polym. Sci. Part A: Polym. Chem. 2006, 44, 6410-6418

Ziegler-Natta Chain (Addition) Polymerization

H

H
C

TiCl4/AlEt3
1-4 atm, rt

Milder conditions than radical polymerization

HDPE (high density poly(ethylene) is 3-10 times stronger than LDPE
Less cross-linking, as terminal DBs less reactive than substituted DBs of radical
polymerization
Termination reaction
H

Cl3Ti

Few monomers polymerized by Z/N

Cl
H Ti Cl
Cl

Ziegler-Natta Addition Polymerization

Isotactic polymerization
TiCl4 / AlR3
R

1-4 atm, rt

R
Cl3Ti

TiCl4 + AlR3

Cl3Ti

AlR2

R + Cl

scomplex

AlR2

Cl

R
Cl3Ti

Cl3Ti

Cl3Ti

pcomplex

Cl3Ti

Cl3Ti

Cl3Ti

Cl3Ti
n

Stereochemistry and Polymers

M any useful pol ym e r s, suc h as pol y( st yr e ne ),

poly(acrylonitrile) and poly(vinyl chloride) are atactic as
normally prepared. Customized catalysts that effect
stereoregular polymerization of poly(propylene) and
some other monomers have been developed, and the
improved properties associated with the increased
crystallinity of these products has made this an
important field of investigation.

Amorphous polymer melts to

a hard rubbery, glassy state

The properties of a given polymer will vary considerably with its tacticity. Atactic poly(propylene)
is useless as a solid construction material, and is employed mainly as a component of adhesives
or as a soft matrix for composite materials. In contrast, isotactic polypropylene is a high-melting
solid (ca. 170 C) which can be molded or machined into structural components.
Because poly(propylene) rope is so light, it is the only rope that floats. For
this reason, it is very popular among ropes for pool makers and water
sports. Also when wet it is flexible and does not shrink.

Step-growth Polymerization
Step-polymers are made by allowing difunctional monomers with
c o m p l e m e n t a r y f u n c t i o n a l g r o u p s t o r e a c t w i th o n e an o t h e r
Condensation between two molecules

HO

+
MeO

OMe

terephthalic acid

C OCH2CH2O
n

OH

ethylene glycol

Poly(ethylene terephthalate)

This is an example of a poly(ester)

The reaction is a transesterification

Using a condensation reaction

PET
Recyclable plastic
bottles and textile
fabrics

Step-growth Polymerization

These are poly(amides) bristles of toothbrishes,

stockings, rope, tires, carpet fibre

Molten nylon spun

into fibres

- H2O
260-280 C
250 psi

First patented by Dupont

MW = 10,000, m.pt. 250 C, fibres stretched (to increase strength) to 4 times their length

Self-Condensation or Ring-Opening Polymerization

Also opened by
cations & anions

First patented by BASF

High temp. to drive off water

Nylon 6 is made by heating caprolactam to about 250 C with about 5-10% water

Step-growth Polymerization
1. Polymers retain their functionality as end groups at the
end of the polymerization
2. Only a single reaction is responsible for polymer formation
3. Molecular weight increases slowly even at high
conversion. This is given by the Carothers equation,
where conversion is (p)

DP =

1
1-p

At 98% conversion, the degree of polymerization is only 50%

Larger chains react only at very high conversion

4. Exact stoichiometric balance and very pure monomers

are required to achieve high molecular weights
5. Equilibrium reactions necessary to remove by-product

Step-growth Polymerization

Step-addition no by-products

180 C

Insulation foam, HP adhesives, sealants,

carpet underlay

Bayer-patented

HO
OH
O

O
O
n

Poly(urethane)

Lower Temp. than condensation reactions

O
CH2

rt

CH2
6

bisdiene

benzoquinone

Cyclic diene held cis is very reactive

e.g. dicyclopentadiene

Chain-growth condensation
CH2N2

BF3

[ CH2 ]n

N2
Impurity found in diazomethane

Time for litter to biodegrade

Product

Time to biodegrade

Paper

2-5 months

Wool socks

1 to 5 years

Plastic coated paper milk cartons

5 years

Plastic bags

10 to 20 years

Nylon fabric

30 to 40 years

Aluminum cans

80 to 100 years

Plastic 6-pack holder rings

450 years

Glass bottles

1 million years

Plastic bottles

Forever

Plastic resin identification codes (1)

Codes

Descriptions

Recycled products

Polyethylene terephthalate (PET, PETE) is clear, tough, and

has good gas and moisture barrier properties. Commonly
used in soft drink bottles and many injection molded. Other
applications include strapping and both food and non-food
containers. Cleaned recycled PET flakes and pellets are in
great demand for spinning fiber for carpet yarns, producing
fiberfill and geo-textiles.

Fiber, tote bags, clothing,

film and sheet, food and
beverage containers, carpet,
strapping, fleece wear,
luggage and bottles.

High Density Polyethylene (HDPE) is used to make bottles for

milk, juice, water and laundry products. Unpigmented bottles
are translucent, have good barrier properties and stiffness,
and are well suited to packaging products with a short shelf
life such as milk. Because HDPE has good chemical
resistance, it is used for packaging many household and
industrial chemicals.

Bottles; pipe, buckets,

crates, flower pots, garden
edging, film and sheet,
recycling bins, benches,
dog houses, plastic lumber,
floor tiles, picnic tables,
fencing.

Polyvinyl Chloride or PVC has excellent chemical resistance,

good weatherability, flow characteristics and stable electrical
properties. The vinyl products can be broadly divided into
rigid and flexible materials. Bottles and packaging sheet are
major rigid markets, but it is also widely used as pipes and
fittings, siding, carpet backing and windows. Flexible vinyl is
used in wire and cable insulation, film and sheet, floor
coverings synthetic leather products, coatings, blood bags,
medical tubing and many others.

Packaging, binders, decking,

paneling, gutters, mud flaps,
film and sheet, floor tiles
and resilient flooring, cables,
mats, cassette trays,
electrical traffic cones,
boxes, garden hose, mobile.

Plastic resin identification codes (2)

Codes

Descriptions

Recycled products

Low Density Polyethylene (LDPE) used predominately in film

applications due to its toughness, flexibility and relative
transparency, making it popular for use in applications where
heat sealing is necessary. LDPE is also used to manufacture
some flexible lids and bottles and it is used in wire and cable
applications.

Shipping envelopes,
garbage can liners, film
and sheet, furniture,
compost bins, paneling,
trash cans, landscape
timber, lumber

Polypropylene (PP) has good chemical resistance, is strong, and

has a high melting point making it good for hot-fill liquids. PP is
found in flexible and rigid packaging to fibers and large molded
parts for automotive and consumer products.

Automobile battery cases,

signal lights, battery
cables, brooms, brushes,
oil bins, funnels, bicycle
racks, trays pallets,
sheeting.

Polystyrene (PS) is a versatile plastic that can be rigid or foamed.

General purpose polystyrene is clear, hard and brittle. It has a
relatively low melting point. Typical applications include
protective packaging, containers, lids, cups, bottles and trays.

Light switch plates, vents,

thermal insulation, desk
trays, rulers, license plate
frames, foam packing,
foam plates, utensils

Other. Use of this code indicates that the package in question is

made with a resin other than the six listed above, or is made of
more than one resin listed above, and used in a multi-layer
combination.

Bottles, plastic lumber

Recycling of plastic containers and wrapping

Chemical Recycling by Eastman Kodak

methanolysis
O

C OCH2CH2O

CH3OH

H+
n

HO

O
C

MeO

+
OMe

PET
These monomers are purified by distillation or recrystallization and used
as feedstocks for further PET film manufacture.

OH

Representative Exam Questions

1. Using one appropriate monomer for each polymerization classification, discuss the mechanism and
kinetics;
(a) Step-growth, b) conventional (non-living) chain (addition), c) living chain (addition) polymerizations.
In your answer give details of reaction conditions and reagents required.
2. (a) Discuss the stability of nitroxide radicals, and there use in living radical polymerizations.
(b) Why is it not possible to control the radical polymerization of methyl methacrylate with nitroxides?
3. How would you prepare the following polymers? Give reaction conditions, reagents and detailed
mechanisms for each polymerization. Name polymers A-D.
n

n
C

n-1
Ph
Ph

m
O

OMe

D : n = 60
: m = 20

4. Draw structures of the polymers obtained from the following reactions;

CO2Me

MeO2C

HO

OH

H+

KOH

5. Give one example of an isotatic polymer and block and alternating copolymer. Provide reactions (with
conditions) and mechanisms for their synthesis.