The phenol + formaldehyde rxn

Network formation
Further reaction under heat & pressure builds up densely
cross-linked network. This is Bakelite, a thermosetting
polymer. Once reaction is complete, material cannot be
reheated and/or reformed

Bakelite
 Bakelite - Material of a Thousand Uses

Clear Bakelite items Phenolic Bakelite telephone

resin/celluloid clock

Bakelite camera Bakelite radio Bakelite microphone

Crosslinking
Take linear polymer chains & link using covalent bonds
 Crosslinking
Ex: rxn of natural rubber or poly(isoprene)

- CH2 CH - CH2 CH2 - CH2 CH2 -

- - 2 - - - -
-C = C - -C = C - -C = C -
CH3 H CH3 H CH3 H

with sulfur - interconnects the chains by reacting

with the double bonds

(vulcanization)
Crosslinking
Tacticity

3 types
isotactic
syndiotactic
atactic
Tacticity

Ex: polypropylene
CH3
propylene monomer: CH2=CH

CH3
upon polymerization: –CH2–C–

H
Tacticity

isotactic

CH3
propylene: CH2=CH
Tacticity

syndiotactic

atactic
Tacticity

Polypropylene - largely isotactic

isotactic character of PP allows "crystallization"

as a result, material can be stiffer

Tacticity

Polystyrene - atactic

Polypropylene - largely isotactic

PVC - largely atactic

(some syndiotactic sequences)
PMMA -atactic
Copolymers

-A-B-B-B-A-A-B-A-B-A-A-A-B-A-B-B-A-B-B-A-A-A-B-
Random Copolymers

-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-
Alternating Copolymers

-A-A-A-A-A-A-B-B-B-B-B-B-B-B-B-B-A-A-A-A-A-A-
Block Copolymers

-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-
A-A-A-A-A-A-A-A-

A-A-A-A-A-A-

Graft Copolymers A-A-A-A-A-A-A-A-A-A-

Blends

miscible immiscible

single phase phase separated

blend
 Molecular weight

CH4 ----------------------------------------- 16 increasing

CH3 - CH3 -------------------------------- 30 molecular weight
Gases
CH3 - CH2 _ CH3 ------------------------ 44
CH3 - CH2 - CH2 - CH3 --------------- 58

Liquids
CH3 - (CH2)6 _ CH3 --------------- 114

"Semi-solid"
CH3 - (CH2)30 CH3 _
--------------- 450

Solids
CH3 - (CH2)30000 _ CH3 ---------- 420030

Increasing
Molecular Weight
 Molecular weight

Chains have different

molecular weights

There is a distribution
 Molecular weight

Is it important?

Tensile Strength Melt Viscosity

Mol. Wt. Mol. Wt.

 Molecular weight

Is it important?

Very important in processing

If viscosity too high, polymer

difficult to process

If too low, an extruded material

won't hold together until it
solidifies
 Blow molding

Step 1: make preform by

extrusion or injection
molding
 Blow molding

Step 1: make preform by

extrusion or injection
molding

Step 2: use air pressure

to inflate preform inside
closed, hollow mold.
Polymer expands to take
shape of cooled mold &
solidifies under pressure
Polymers are different
 Polymers are different

• Normal crystalline materials

– Either crystalline (~100 %, neglecting
defects ) or amorphous at a particular
temperature
– Melt at a sharp, well-defined temperature

• Crystallizable polymers
– Never 100% crystalline
– Melt over a range of temperatures