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
H C

Plus

Formaldehyde
C H H

H C

C

C H C

C H

H

Thermoset Types
• Phenolics

Crosslinking
• Reactive Groups—Amino plastics
H N R N H

O

Formaldehyde

Amine
H H

Plus

C H H

Amine plastics – clear adhesive

Chipboard

Crosslinking as Polymers are Formed
H
Three active sites

N C

H

Plus
Formaldehyde

N H C N H N
Melamine

N C N H H

O

C H H

Crosslinking as Polymers are Formed

Melamine Formaldehyde

Water

Thermoset Types
• Melamine Plastics

Crosslinking as Polymers are Formed

Melamine Formaldehyde

Water

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 C R C H
Carbon-carbon Double bond

Plus
R1

O R O
Initiator (usually peroxide)

R1

Thermoset Types
• Unsaturated Polyesters

Crosslinking Mechanism for Thermoset Polyesters
O H O C C H H C O C O H

Polyester
O H O C C H
H C C H H

H C

O C O H

Styrene (large quantities)
CH HC C CH CH CH

Peroxide
O R O R1

Crosslinking – Heat
O H O C C H H C O C O H

O H O C C H

H C

O C O H
CH HC CH CH CH

Peroxide breaks apart

H C C H

C

H

Crosslinking – Approach of styrene
O H O C C H H C O C O H

O H O C C H

H C

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

H

Crosslinking – bond to styrene
O H O C C H O H O C C H H C O C O H H C O C O 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 H O C C H H C O 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 H C H C O C O H

New free radical

H

O

C

CH

New bond
H C C H

HC C CH

CH CH

H

Problems: Polymers not lined up, steric interference Solution: Styrene

Crosslinking– approach of styrene
O H O C C H
HC H C C H H C CH

H C

O C O H

CH CH CH

Crosslinking– activation of styrene
O H O C C H H C O C O H

Styrene's double bond opens, allowing two new free radical sites

Crosslinking – bonding of styrene

New bond

CH HC CH

H C C H

C CH

CH

H

Double bond opens but can't create a bond with any other open bond because of steric 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 N R N H

Plus
H
Epoxy Rings

H

Hardener (amine shown)

Thermoset Types
• Epoxies

Vinyl Esters (VE)

Polyimides
H O O
H C

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

C C R N C C

C C

C
C O

N C C C

R1

O H

O

Condensation Imide

Carbon-carbon Double bond Imide

React with addition reaction

Thermoset Types
• Imides

Crosslinking
• Reactive Groups—Polyurethanes

H O

R O

H

Plus
H O C N R

Diisocyanates

H N C H O

Polyols

H

Thermoset Types
• Polyurethanes

Crosslinking Between two Existing Polymer Chains
H H

O
O H C C O

H C H C

O C O H

H
H H H

O

C

Polymerization Active Sites

Crosslinking Active Site

Thank You