Lecture # 4

MONOMERS: BUILDING BLOCKS FOR POLYMER MANUFACTURE: The paraffins ((like methane ) are unable to polymerize due to lack of a double bond-hence they are not considered to be
monomers. Ethylene, on the other hand, represents the simplest and most commonly used monomer, essentially due to the existence of an aliphatic double bond that starts the polymeric chain.

 In butadiene:

X= halogens,PVC CH3 ,Propylene CN ,acrylonitrile Phenyl gp(bz ring) ,styrene

Polymerization Reactions Step

(aka: Condensation)

Chain
(aka: Addition)

Free Radical

-Ionic -Coordination -Group Transfer

Polymerization Mechanisms
1- Polymerization by condensation: a.is the formation of polyamide (in our case Nylon 6-6) by reacting a di-acid with a diamine.

b.Let us consider a condensation reaction of monofunctional groups, like classical esterification:

Condensation Polymerization Characteristics

Gives off a small molecule (often H2O) as a byproduct Stepwise polymerization

long reaction times

Bifunctional monomers linear

polymers

Trifunctional monomers crosslinked (network) polymers

Condensation Polymerization
Examples:
Polyesters
Nylons

Polycarbonates

Polyesters from a hydroxy-acid

Acid and base functionality on one monomer:

e.g., n . HO-CH2CH2CH2CH2COOH -(-CH2CH2CH2CH2COO-)n- + nH2O

General reaction:

n . HO-R-COOH -(-R-COO-)n- + nH2O

Condensation Polymerization Esterification

Polyester from a di-alcohol and a di-

acid

Example (Callister eq. 16.8):

Another polyester: PETE

terephthalic acid + ethylene glycol n.HOOC-C6H4-COOH + n.HO-CH2CH2-OH -(-OOC-C6H4-COO-CH2CH2-)n + 2nH2O

Nylon 6 from polymerization of an amino acid

acid and base groups on one monomer

H2N-(CH2)5-COOH

n H2N-(CH2)5-COOH (-(CH2)5-CONH)n + nH2O

6-carbon monomer 6-carbon mer

Nylon 6,6 2 monomers: 6-carbon

diamine + 6-carbon diacid

hexamethylene diamine + adipic acid

Problem Nylon 6,6

Calculate the masses of hexamethylene diamine and adipic acid needed to produce 1000 kg of nylon 6,6.

Solution:
The chemical reaction is: nH2N-(CH2)6-NH2 + nHOOC-(CH2)4-COOH -(-HNOC-(CH2)4-CONH-(CH2)6-)n + 2nH2O

The masses are in proportion to molecular weights. Per mer of nylon

6,6:

C6H16N2 72+16+28

+ +

C6H10O4 72+10+64

C12H22O2N2 226 103 kg

2H2O + + 2x18 36

144+22+32+28

116 + 116x103kg 226 513 kg HMDA + byproduct

146 146x103kg 226 646 kg adipic acid

Note: 159 kg of H2O