Novel Polymers

Polymers (macromolecules) are long chain organic molecules created by many

repeating units called monomers. E.g., necklace made from many small beads
(monomers).
Many synthetic polymers - called plastic originate from Greek word plastikos
means suitable for molding, shaping or malleable. Molecular weight is
important in determining many physical properties. For examples, transitions
temperatures for liquids -- waxes -- rubbers -- solids and mechanical
properties as stiffness, strength, viscoelasticity, toughness, and viscosity.

Applications: common house hold like utensils to replacement of human

body parts, packing, wrapping, building materials , textiles, TV's, CD's,
automobiles, coat metal wires and many others.
Natural polymers: Proteins - silk, collagen, keratin.
Carbohydrates - cellulose, starch, glycogen
DNA - RNA
Rubber (hydrocarbon base) and silicones (alternating silicon and oxygen).
Hideki Shirakawa said that polymer (polyacetylene) can be made conductive
almost like a metal.

What is Polymerization? Monomers------- polymers

------

Common Polyolefins
Monomer
Ethylene
CH3
Propylene
Ph
Styrene

Polymer
Polyethylene

Polypropylene

Polystyrene

CH3

H3C

Vinyl Chloride
F2C CF2
Tetrafluoroethylene

CH3

CH3 CH3 CH3 CH3 CH3 CH3 CH3

Ph

Ph

Ph

Ph

Cl
Poly(vinyl chloride)

Repeat unit

Cl

F3C
Poly(tetrafluoroethylene): Teflon

Cl

F2
C

C
F2

Cl

F2
C

C
F2

Cl

F2
C

C
F2

CH3

Ph

Ph

Ph
CH3

Cl

F2
C

C
nF
2

Cl

F2
C

C
F2

Cl

F2
C

C
F2

CF3

Polyesters, Amides, and Urethanes

Monomer
HO2C

CO2H

Terephthalic
acid
O
O

Polymer
O

OH

HO
Ethylene
glycol

Poly(ethylene terephthalate

HO

Nylon 6,6

CO2H H2N

Terephthalic
acid

OCN

H2
C

NH2

1,4-Diamino
benzene

NCO

4,4-diisocyantophenylmethane
O
HO

H
N

H2
C

Kevlar

HO

Ester

O
HO2C

H2 H2
O C C O H

HO

NH2
OH H2N
4
1,6-Diaminohexane

HO
4
Adipic Acid

O
4

N
H

N
H
Amide
4

H
n

H
N

H
N H
n

OH
HO
Spandex
Ethylene
glycol
O
H2 H2
H
N
O C C O H
n

Urethane linkage

Natural Polymers
Polymer

Monomer

Polyisoprene:
Natural rubber

Isoprene

H OH
HO
HO

OH
H
H
-D-glucose
O

H3N

OH

Poly(-D-glycoside):
cellulose

OH
Nucleotide
Base = C, G, T, A

oligonucleic acid
DNA

O
HO

H3 N

H
N

R1

Rn+1
DNA

Base

HO
H

Polyamino acid:
protein

R
Amino Acid
O
O P O

H OH

HO

OH
H

H
N
n

OH

OH
Rn+2

O
O P O

O
O

DNA

Base

Classification of Polymers based on monomer units

(i) Homopolymers - consist of chains with identical bonding linkages to
each monomer unit. This usually implies that the polymer is made from all
identical monomer molecules. E.g., -[A-A-A-A-A-A](ii) Copolymers - consist of chains with two or more linkages usually
implying two or more different types of monomer units.
a. Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-A-B
b. Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-A-B
c. Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B-

Classification based on the physical property & heating:

(i) Thermoplastics - plastics that soften when heated and become firm again
when cooled. This is the more popular type of plastic because the heating and
cooling may be repeated.
(ii) Thermosets - plastics that soften when heated and can be molded, but
harden permanently. They will decompose when reheated. For example,
Bakelite used in toasters, handles for pots and pans, dishes, electrical outlets
and billiard balls.

Classified based on the reaction mode

(i) Addition (chain-growth) Polymers - the monomer molecules bond to each
other without the loss of any other atoms. Alkene/alkyne monomers are the
biggest groups of polymers in this class. Reactive intermediates formation take
place.
M.Wt.: quite high (e.g., 46 x 106 for polystyrene)
(ii) Condensation (step-growth) Polymers - two different monomer combine with
the loss of a small molecule, usually water. Monomers contain functional groups
capable of reacting with each other. No reactive intermediates formation take
place. For example, polyesters, polyamides (nylons), polyurethanes, etc.
M.Wt.: usually < 50,000 g/mol

Addition:onemonomeratatime
Alsocalledchaingrowth.

Condensation:anythinggoes!
Alsocalledstepgrowth.

Two general ways of preparing polymers

1. Addition Polymerization:
2. Condensation Polymerization

For example, Polyethylene Glycol:

Addition Polymerization
Based on reaction mechanism in addition polymerization:
(i) Radical reaction path;
(ii) Anionic reaction path and
(iii) Cationic reaction path.

Three consecutive reaction steps takes place for the polymerization:

a. Initiation step;
b. Propagation step and
c. Termination step.

1. Free Radical Polymerization:

Initiation step:

Propagation step:

Termination step:

Typical Radical Initiators:

For examples:

Copolymerization:

2. Cationic Polymerization: Initiated using a proton (H+), a Lewis acid or a

carbocation (R+, generated from R-X + Lewis acid, AlCl3, BF3, etc).
For example,

3. Anionic Polymerization: Initiator is an anion (often a carbanion).

For example:

Block Copolymerization

What are Ziegler-Natta Catalysts? (Nobel Prize in Chemistry in 1966)

K. Ziegler (1953) found that Ni-Et3Al dimerized olefins. This prompted a survey
for other transition metals (TMs). Group IV metals (Ti & V)- effective catalysts for
ethylene polymerization.
Ziegler-Natta catalyst is composed of at least two parts: TM part - the catalyst
and a main group metal alkyl compound (usually Al-alkyl) - the co-catalyst.
A 3rd component is used to control stereo regularity either be incorporated into
the catalyst as internal donor (aromatic esters) or external donor (alkoxysilanes
& hindered amines).
This catalyst system demonstrates that the stereo-regular polymerization of
polypropylene could be achieved.

Coordination Polymerization: Ziegler-Natta Catalyst

Ziegler-Natta catalysts are used to produce the following classes of polymers

from alpha olefins:
1. High density polyethylene (HDPE)
2. Linear low density polyethylene (LLDPE)
3. Ultra-high molecular weight polyethylene (UHMWPE)
4. Polypropylene (PP)--homopolymer, random copolymer and high impact
copolymers
5. Thermoplastic polyolefins (TPOs)
6. Ethylene propylene diene monomer polymers (EPDM)
7. Polybutene (PB)

Condensation Polymerization
Making ester linkages Polyesters
Making amide linkages Polyamides
For example, Polyesters

Analogously:

Ring-Opening Polymerization

Polyamides (Nylons):

Ring Opening of Lactams:

Polyureas:

Analogs Polyurethanes

Stereochemical control of Polymer Microstructure

n

CH3

CH3 CH3 CH3 CH3 CH3 CH3 CH3

With so many stereocenters, the stereochemistry can be complex. There are

three main stereochemical classifications for polymers.

Atactic: random orientation

Isotactic: All stereocenters have same orientation

Syndiotactic: Alternating stereochemistry

Tacticity
(order of placement of side groups)

Ease of
crystallization

Tacticity affects the physical properties

-Atactic polymers will generally be amorphous, soft, flexible materials
-Isotactic and syndiotactic polymers will be more crystalline, thus harder
and less flexible
Polypropylene (PP) is a good example
-Atactic PP is a low melting, gooey material
- Isoatactic PP is high melting (176), crystalline, tough material that is
industrially useful
-Syndiotactic PP has similar properties, but is very clear. It is harder to
synthesize

Polyurethanes (PU)
Generalized polyurethane reaction
PU reaction mechanism catalyzed by a tertiary amine

PU reaction mechanism:

carbon dioxide gas formed when reacting with water

Summary PU reaction:

STRETCHABLE Fibres

Commodity Polyolefins
Polyethylene
High Density (1954)
HDPE
Bottles, drums, pipe, conduit, sheet, film
Low Density (1939-1945)
LDPE
Packaging Film, wire and cable coating, toys, flexible bottles, house
wares, coatings
Linear Low Density (1975)
Shirt bags, high strength films

LLDE

Commodity Polyolefins
Polypropylene (1954)
PP
dishwasher safe plastic ware, carpet yarn, fibers and ropes, webbing,
auto parts
Polyisobutylene (1940)
PIB
inner tubes, flexible adhesives, raincoats

Commodity Vinyl Polymers

Polystyrene (1920)
PS
Styrofoam, clear plastic cups
envelop windows, toys
Cl

Poly(vinyl chloride) (1927)

Cl

Cl

Cl

PVC
garden hose, pipe, car trim, seat covers, records, floor tiles

Semi-Commodity Polymers

CO2CH3

Poly(methyl methacrylate) (1931)

CO2CH3
CO2CH3

CO2CH3

CO2CH3

PMMA
plexiglass, embedding resin, resist for X-ray applications

Polytetrafluoroethylene. (1943)
teflon, non stick cookware, no grease bearings,
pipe-seal tape

F
F

F
F

F
F

F
F

F
F

F
F

F
F

F
F

Commodity Condensation Polymers

O
N

Nylon 6
bearings, molded parts
carpet yarn
marine rope
cooking/boiling bags

Nylon 66 (1939)
bullet-proof vests, clothes, Fibers, tire cord,
fishing

line, canoes,

kayaks,

fishing poles and tennis racquets.

sailboats,

Commodity Condensation Polymers

Polyester (1941

C
O

PET, dacron, mylar, kodel

fibers, film-backing, magnetic tapes, soft drink bottles, tire cord, moldings

Polycarbonate (1957)

O
O

PC, Lexan
shatter proof glass, CD-disks, car doors and roofs, appliance housings

C
O

Conducting polymers or Intrinsically conducting polymers (ICPs)

(polymersplasticsbeingsomehowtheoppositeofmetals)
Organic electrically conductive polymers: poly(acetylene)s, poly(pyrrole)s,
poly(thiophene)s, poly(aniline)s, poly(fluorene)s, poly(p-phenylene sulfide). The
melanin pigment in animals is a mixed copolymer of polyacetylene, polypyrrole,
and polyaniline. Some fungal melanins are pure polyacetylene. (A. J. Heeger, A.
G. MacDiarmid, H. Shirakawa 2000 (Nobel Prize).
Oxidation with Cl2, Br2 or I2 vapor made polyacetylene films >109 times
conductive than original called doping. The doped form of polyacetylene
had a conductivity of 105 Siemens/meter, higher than any known polymer like
teflon -1016S m1 and silver and copper 108 S m1.

The halogen doping that transforms polyacetylene to a good conductor of

electricity is by oxidation (p-doping). Reductive doping (n-doping) is also
possible using, e.g., an alkali metal.
[CH]n + 3x/2 I 2 .......> [CH]n x+ +xI3

oxidative doping

[CH] n + xNa > [CH]n x + xNa +

reductive doping

The doped polymer is thus a salt. However, it is not the counter ions, I 3 or Na+,
but the charges on the polymer that are the mobile charge carriers.
By applying an electric field perpendicular to the film, the counter ions can be
made to diffuse from or into the structure, causing the doping reaction to
proceed backwards or forwards. In this way the conductivity can be switched
off or on.

Types of Conducting Polymers: a. Electron- Conducting Polymers

b. Proton- Conducting Polymers c. Ion- Conducting Polymers

Radical cation (polaron) formed by removal of one electron on the 5 th carbon

atom of a undecahexaene chain (a b). Polaron migration shown in c e.

What makes a material conductive?

In many materialscrystals, stretched

polymers or liquid
crystals,
macroscopic
properties Strength/optical/

3D

2D

electrical properties
generally depend on
direction said

1Dformsofcarbonmaterials

anisotropic.

108 -107S m1

103 -102S m1

Doping cis-polyacetylene with AsF5 resulted in an increase of conductivity by a

factor of 1011. The high conductivity found opened up the field of plastic
electronics.
Applications:
Doped polyaniline - conductor and for electromagnetic shielding of electronic
circuits.
Polyaniline -a corrosion inhibitor.
Poly(ethylenedioxythiophene) (PEDOT) doped with polystyrenesulfonic acid as
an antistatic coating material to prevent electrical discharge exposure on
photographic emulsions and serves as a hole injecting electrode material in
polymer light-emitting devices.
Poly(phenylene vinylidene): have been major candidates for the active layer in
pilot production of electroluminescent displays (mobile telephone displays).
Poly(dialkylfluorene): as the emissive layer in full-color video matrix displays.
Poly(thiophene): field-effect transistors: for supermarket checkouts.
Poly(pyrrole): tested as microwave-absorbing stealth (radar-invisible) screen
coatings and active thin layer of various sensing devices.

Electroluminescent polymers second-generation conductive polymers