Many + Parts

This name hints at how polymers are made

Latin: Plasticus, that which This name honors plastics useful property of being can be molded
easily molded

The word, polymer, implies that polymers are constructed from pieces (monomers) that can be easily connected into long chains (polymer). When you look at the above shapes, your mind should see that they could easily fit together.

Cotton fiber is mostly cellulose, and cellulose is made of chains of the sugar, glucose linked together a certain way.

Polymers
Polymer: High molecular weight molecule made up of a small repeat unit (monomer).
A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A

Monomer: Low molecular weight compound that can be connected together to give a poymer Oligomer: Short polymer chain Copolymer: polymer made up of 2 or more monomers
Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-A-B Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-A-B Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B

Types of Polymers
Polymer Classifications
Thermoset: cross-linked polymer that cannot be melted (tires, rubber bands) Thermoplastic: Meltable plastic Elastomers: Polymers that stretch and then return to their original form: often thermoset polymers Thermoplastic elastomers: Elastic polymers that can be melted (soles of tennis shoes)

Polymer Families
Polyolefins: made from olefin (alkene) monomers Polyesters, Amides, Urethanes, etc.: monomers linked by ester, amide, urethane or other functional groups Natural Polymers: Polysaccharides, DNA, proteins

Common Polyolefins
M onom er
E th yle n e CH3 P o lyp ro p yle n e P ro p yle n e Ph P o lystyre n e S tyren e Cl P o ly(vin yl ch lo rid e ) V in yl C h lo rid e F 2C CF2 F 3C P o ly(tetra flu o ro e th yle n e ): T e flo n F2 C C F2 F2 C C F2 F2 C C F2 F2 C C nF 2 F2 C C F2 F2 C C F2 C F3 Cl Cl Cl Cl CH3
n

P o lym e r
P o lye th yle n e H 3C CH3
n

R e p e a t u n it CH3
n

CH3

CH3

CH3

CH3

CH3

CH3

CH3 CH3

Ph

Ph

Ph

Ph

Ph

Ph

Ph

Cl

Cl

Cl

T etra flu o ro e th yle n e

Polyesters, Amides, and Urethanes

M o n o m er
O H O 2C T ereph thalic ac id C O 2H HO OH E thyle ne glyco l P oly(e thylen e tere phtha late E ste r HO

P o ly m er
O O H2 H2 C C O H
n

O NH2 O H H 2N 4 1 ,6-D ia m in o h e xa n e N ylo n 6,6 HO

O
4

HO 4 A d ip ic A cid

N H O

N 4 H A m id e H N

H
n

O H O 2C T e re p hth a lic a cid OCN H2 C C O 2H H 2N 1 ,4 -D ia m in o b en ze n e NCO NH2 K e vla r HO

H N

H
n

HO

OH E th yle n e g lyco l O H N O S p a n d ex H2 H2 C C O

4,4 -diiso cyan to p h e n ylm e tha n e O HO H N H2 C

H
n

U re th a n e lin ka g e

Natural Polymers
M onom er P o ly m e r
Iso p re ne H OH HO HO H O OH H H -D -g lu co se O H 3N O P o lya m in o a cid : p ro te in H 3N R1 H OH P o ly( -D -glyco sid e ): ce llu lo se H P olyiso p re n e : N a tu ra l rub b er H OH O HO H H O H OH H OH
n

H N

O R n+1
n

H N

O OH R n+2

R A m in o A cid

 Types of Polymerization mechanisms: 1. Addition polymerization. 2. Condensation polymerization. 1) Addition polymerization :

This kind of polymerization is typified by the presence of a carbon carbon double bond in the monomer.
 This reaction takes place in presence of catalyst or light, heat.

 A monomer is a small molecule that makes up a polymer. The monomer molecules usually contain one or two doubles bonds During addition of polymerization the double bond breaks and becomes a single bond. Ex : polymerization of ethylene, pvc, poly styrene, poly acrylonitrile.

Polymerization of PVC

Mechanism of addition polymerization : Chain growth polymerization: It involves the linking together of molecules incorporating double or triple. These unsaturated monomers have extra internal bonds that are able to break and link up with other monomers to form the repeating chain. It involves 3 steps: 1. Chain initiation step 2. Chain propagation step 3. Chain termination step

1.Chain Initiation step :  Initiators are chemicals that produce the chain initiating species, the chain initiators under go homolytic cleavage when excited.  E.g.: acetyl peroxide, benzoyl peroxide.

2.Chain propagation step :  Free radicals combines with another monomer to give a new radical and this radical will again with a monomer to give a longer chain radicals.  This process goes on continuing producing a high polymer.

3.Chain termination step :  Termination of the propagation of polymer chain can happen either by coupling reaction or disproportionation.
hv/ heat
R O O R

2 R *

O2

PROPAGATION STEP R* + CH2=CH2 R-CH2-CH2* + CH2 = CH2 R-CH2-CH2* R-CH2-CH2-CH2-CH2*

.............. TERMINATION STEP 2 R- (CH2 -CH2)n- CH2-CH2* + CH2-CH2*

R- (CH2 -CH2)n- CH2-CH2*

R-(CH2-CH2)n-R

Addition Polymerization
In * A In itiatio n In A A A A* nA P ro p a g a tio n In A A A A
n

A*

*A *A A A
m

A
m

In

A A*

A
n

In

A B

A A

A A
m

A
n

A A

In

A
n

A
m

C o m b in a tio n A D isp ro p o rtio n a tio n

C h a in T ra n s fe r N e w re a ctive site is p ro d u ce d

T erm in atio n R eactive site is consu m ed

Types of Addition Polymerizations

A n io n ic
Ph C 3H 7 Li L i+ Ph

n Ph C 4H 9 Ph
n

Li + Ph

C 4H 9

R a d ic a l
Ph P hC O 2

n
P hC O 2 Ph

Ph

P hC O 2 Ph

C a tio n ic
Ph C l3 A l O H 2

Ph

H Ph H O A lC l 3

Ph

H Ph

H O A lC l 3
n

Ph

2) Condensation polymerization:

A condensation polymer generally involves 2 monomers that have different functional groups. They also involve the elimination of water or another small molecule. Hence the term condensation polymer
 E.g.: formation of urea formaldehyde, nylon 6,6.

Step-Growth Polymerization
n n S tage 1 C on su m p tion of m o no m e r

S ta ge 2 C o m bin atio n of sm all fra gm e nts

S ta ge 3 R e actio n of oligom e rs to give high m o lec ula r w e ight po lym er

Polymerization of polyester
Polymerization of polyester

Mechanism in condensation polymerization Step growth polymerization: Step-growth polymers are defined as polymers formed by the stepwise reaction between functional groups of monomers. Most stepgrowth polymers are also classified as condensation polymers. This rate is lower than chain growth polymerization.

3) Co polymerization: Is a reaction that yields a polymer made of different monomer units E.g.: Bunna-s rubber, poly acrylo nitril-co-vinyl chloride polymer