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 resin/celluloid clock

Bakelite telephone

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

CH2 - CH2 CH2 - CH2 CH2 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: CH2C 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 Polypropylene PVC PMMA

- atactic - largely isotactic - largely atactic -atactic

(some syndiotactic sequences)

Copolymers
-A-B-B-B-A-A-B-A-B-A-A-A-B-A-B-B-A-B-B-A-A-A-BRandom Copolymers

-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-BAlternating Copolymers

-A-A-A-A-A-A-B-B-B-B-B-B-B-B-B-B-A-A-A-A-A-ABlock Copolymers

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

-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-BA-A-A-A-A-A-A-A-A-AA-A-A-A-A-AGraft Copolymers

Blends

miscible

immiscible

single phase

phase separated blend

Molecular weight

CH4 ----------------------------------------CH3 - CH3 -------------------------------Gases CH3 - CH2 _ CH3 -----------------------CH3 - CH2 - CH2 - CH3 --------------CH3 - (CH2)6 _ CH3 CH3 - (CH2)30 _ CH3
Liquids

16 30 44 58 114

increasing molecular weight

--------------"Semi-solid"

--------------Solids

450

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