Thermoset Materials

MFG 355
 Introduction
• Thermoplastics vs Thermosets
– Thermal properties
– Strength
– Uses
– Processing
Viscosity and Thermal Control
during Crosslinking
 General Properties of Thermosets
• Strength
• Flexibility
• Thermal
• Creep
• Ability to reinforce
• Ability to cure at room temperature
 Formaldehyde Resins
• Phenolic
• Urea formaldehyde
• Melamine formaldehyde
 Crosslinking
• Reactive Groups—Phenolics
H O

O Phenol Plus Formaldehyde

C

H C H H H

C C

C C

H C H

H
 Thermoset Types
• Phenolics
 Crosslinking
• Reactive Groups—Amino plastics
O
H R H
Formaldehyde
N N
C
Amine Plus
H H
H H
Amine plastics – clear adhesive

Chipboard
 Crosslinking as Polymers are
Formed
H H
N Plus
Three
active
sites
C Formaldehyde
O
N N

C
C C H
H
N N N H H

Melamine
H H
Crosslinking as Polymers are
Formed

Melamine Formaldehyde Water

 Thermoset Types
• Melamine Plastics
Crosslinking as Polymers are
Formed

Water
Melamine Formaldehyde
H H
O
 Polyester Thermosets (TS) or
Unsaturated Polyesters (UP)
• Largest group of thermosets
• Most like to be reinforced with fiberglass
 Crosslinking
• Reactive Groups—Unsaturated polyesters
H
Plus
C R1
R C
Carbon-carbon
H
Double bond O R1
R O
Initiator
(usually peroxide)
 Thermoset Types
• Unsaturated Polyesters
 Crosslinking Mechanism for
Thermoset Polyesters
O O
H

H O C C C C O H

Polyester
O O
H Styrene
H O C C C C O H (large quantities)
CH
HC CH
H
H C CH
C CH

C
Peroxide H H

O R1
R O
 Crosslinking – Heat
O O
H

H O C C C C O H

O O
H

H O C C C C O H
CH
H HC CH

Peroxide H C CH
breaks C CH
apart
C
H H
 Crosslinking – Approach of styrene
O O
H

H O C C C C O H

O O
H

H O C C C C O H

H CH
HC CH

H C CH
C CH

C
H H
 Crosslinking – bond to styrene
O O
H

H O C C C C O H

O O
H

H O C C C C O H

H When styrene's double bond

breaks, one end forms a free
radical

Half of peroxide bonds with other end of broken styrene molecule

Crosslinking – approach to polymer
O O
H

H O C C C C O H

Styrene free radical

causes the polymer's
double bond to break
and allows it to accept a
new pi bond
 Crosslinking– bonding to polymer
O O
H

H O C C C C O H
New free
radical
H

CH

New bond HC CH

H C CH
C CH

C
H H

Problems: Polymers not lined up, steric interference

Solution: Styrene
Crosslinking– approach of styrene
O O
H

H O C C C C O H

H
CH
HC CH

H C CH
C CH

C
H H
Crosslinking– activation of styrene
O O
H

H O C C C C O H

H
Styrene's
double bond
opens, allowing
two new free
radical sites
 Crosslinking – bonding of styrene

New bond Double bond

opens but
can't create a
CH bond with any
HC CH
other open
H
C
C
CH
CH
bond because
C
of steric
H H
effects

Problems: Polymers still not lined up, steric interference

Solution: Still more styrene

Crosslinking – bonding of 2nd styrene
Free radical

New bond
Crosslinking– bonding with 2nd polymer
Up to 8 styrenes might be needed in the
bridge

New bond
Crosslinking– bonding with 2nd polymer

Etc.
Crosslinking– more styrene
Crosslinking– more styrene
Crosslinking–bonding to 3 polymer
rd
Laminating Resins
 Additives to Thermoset Polyesters

Fillers like Calcium Carbonate

Tougheners like rubbers
Antioxidants and UV stabilizers
Reinforcements
Molding Compounds
Molding Compounds
 Crosslinking
• Reactive Groups—Epoxies
H R H

N N
Plus
H H
Epoxy Rings

Hardener
(amine shown)
 Thermoset Types
• Epoxies
Vinyl Esters (VE)
 Polyimides H

H
C
O O
O
H C O H
C
C C
C C C
C C
N
C
R N N R1 N
R C
O H
C C
C C C
C
O

O O
H

Carbon-carbon
Condensation Imide Double bond Imide

React with addition reaction

 Thermoset Types
• Imides
 Crosslinking
• Reactive Groups—Polyurethanes
H R H Plus Diisocyanates

O O H H

O N N O
C R C

Polyols H H
 Thermoset Types
• Polyurethanes
 Crosslinking Between two Existing
Polymer Chains
H H

O O
H
O C C O
H O C C C C O H
H H
H H H

Crosslinking
Polymerization Active Site
Active Sites
Thank You