Unsaturated

Polyesters
Dr. Saad Nauman
Advantages
Most common matrix material for PMCs
Cost: 25% less than vinyl esters and 33-
50% less than epoxies
Ease of cure
Ease of molding
Advantages
Wide range of properties
Wide experience base
Basic building block of composite industry
worldwide
Largest market volume of composites
industry
Disadvantages
Poor durability
Brittleness
Concerns related to health hazards
Potential pollutant
Applications
Automobile parts
Small Boats; in hull and deck
Sailing ships: Mast and other fittings
Pump housings
Motor shrouds
Tub and shower units
Spas
Building panels
Industrial tanks and pipes for non corrosive
materials
Thermoset vs. thermoplastic
polyesters
Thermoset polyesters (TP) or unsaturated
polyesters (UP):
have a reactive unsaturated site
Thermoplastic polyesters:
Polyethylene Terephthalate (PET)
UP Manufacturing
Two steps in making and using UP resins
Polymerization: which results in the
manufacturing of UP
Cross-linking or curing: carried out during
molding
Polymerization of unsaturated
polyesters
Condensation polymerization of
monomers
Atleast two difunctional monomers
polymerize
Links formed as a result of polymerization
reaction are ester groups
Polymerization mechanism
Glycols (two alcoholic groups) + Diacid (two carboxylic
groups) Alkyd (alcohol+acid) or UP/TP
Molecular weight or chain length is optimized by
controlling polymerization reaction
Reactions terminate
when concentration of monomers reaches certain minimum
value
By lowering the temperature
By adding a quenching agent (reacts with the end of the chain
but has no active site)
Monomer reaction
+
Glycol
Diacid

Ester

+
Water
New molecule reacts with new
monomers
+
Glycol
Diacid

+ Water
Ester linkages
Polymer properties
Presence of ester groups:
Sensitivity to polar solvents such as water
especially at high temperatures
At 200F polyester resins absorb significant
quantity of water and lose strength
At lower temperatures the effect is not
detrimental
Polymer properties
Acid Number
Unreacted amount of acid monomer
Gives the extent of polymerization
Determined using techniques such as titration
High acid number is detrimental to chemical
resistance and stability of molecular weight
High acid number: may be because of premature
termination of reaction or too high concentrations w.r.t
glycol
Slight excess of glycol is added to keep acid
number below certain value
Polymer properties
Processing viscosity
Monitored during polymerization
Measure of extent of polymerization reaction
Typical MW: 800-10,000
Viscosity range: 50 centipoise to 4000
centipoise
High performance UP: high viscosity/MW and
are difficult to process
Polymer properties
Choice of specific type of diacid, glycol
and specialized monomers
Location of unsaturation: mostly diacids
contain unsaturation
Olefinic unsaturation or carbon-carbon
double bonds in aliphatic compounds
Diacid Monomers
Fumaric
acid

Maleic acid

Maleic
anhydride
Downside of unsaturation sites
Too many unsaturation sites high level of cross
linkages brittleness in the final composite
part
Cross linkage needs to be limited
1. Vary the concentrations and conditions of cross
linking (controlled by molder)
2. Replace some of the unsaturation sites with
saturated sites
Mixing two types of diacid monomers (controlled by resin
manufacturer)
Saturated diacid monomers
Orthophthalic acid

Orthophthalic
anhydride

Isophthalic acid
Saturated diacid monomers
Terephthalic acid High thermal resistance (HDT)

Adipic acid Aliphatic

Less rigid
Less strong
Tougher
Better resistance to UV and Oxygen
Saturated diacid monomers
Tetrabromophthalic Effective in imparting flame
resistance due to the presence
anhydride of halogens

Chlorendic acid Same as above

Glycol monomers
Ethylene Glycol Low cost

Propylene Glycol
Tougher and flexible
Glycol monomers
Diethylene Glycol Even more flexible and tough due to
longer and flexible chains

Neopentyl Glycol Tougher and flexible

Glycol monomers
Bisphenol A Both the aliphatic and aromatic
characteristics are present
Strong and tough
More expensive
Crosslinking steps

C C

Generic Unsaturated polyester

Crosslinking steps Organic peroxides split apart in
Initiator I two segments each having an
unpaired electron

C C

Attack of initiator
Curing reaction begins when small amount (1.5-2%) of cross linking agent is
added
Most common initiator is an organic peroxide
Organic peroxides form free radicals
These radicals attack loosely held electrons in one of the carbon-carbon
double bonds
Crosslinking steps
Initiator I

C C

This electron migrates to the

second atom where it
becomes a new free radical

Attack of initiator
Crosslinking steps Initiator Carbon
I bond formation (2
electrons)

C C

Unshared electron
Can be bonded to
any loosely held
electron

Radical generation
Crosslinking steps Initiator Carbon
I bond formation (2
electrons)

C C
Unshared
electron

C C

Styrene molecule (Reactive diluent) is attacked

at double bond site
Styrene is added to the mix as co-reactant or solvent
Styrene is a small molecule
Can move around freely between the polymer chains
These are called reactive diluents
Crosslinking steps Initiator Carbon
I bond formation (2
electrons)

C C

C C

Unshared
electron
Formation of a new bond and a new free
radical
A new free radical is formed on Styrene
The most probable reactant because of size and mobility is another Styrene
molecule
Crosslinking steps Styrene encounters a
neighboring polymer having
I an unsaturation site

C C
Small chain pendant of
Styrene molecules
New bonds (Cross links)
Styrene group

C C

New free radical available for further reactions

Complete crosslinking through Styrene
bridge
Crosslinking
The free radical formation continues until most
or all of the polyester molecules are crosslinked
Process terminates when free radical reacts with
something other then Styrene or polymer
unsaturation site
Oxygen
Contaminant
Other peroxide (free radical segment)
Concentration of above is critical in determining
extent of crosslinking
Exotherm
Heat liberated during the curing reaction
Important in setting up the curing
conditions
Compensation for exotherm should be given
or the reaction will proceed to quickly
Results of fast curing: fire, degradation, loss
of properties, incomplete crosslinking
Dimensional thickness of the molded part
Peroxide initiators
MEKP: Methyl Ethyl Ketone Peroxide
Can be chemically as well as thermally activated
Most room temperature cures involve MEKP
Peroxides have tendency to decompose
Need to be refrigerated in small quantities
Peroxides are characterized by
Temperature of activation
Types of chemicals that affect the activation reaction
Resin types it is used with
Peroxide initiators
Many unsaturation sites are attacked
simultaneously
Only a few initiator molecules are required
Initiator quantity required: 1.5-2.0% of total
resin weight
Crosslinking agents
Also known as
Bridgemolecules
Co-reactants
Co-monomers
Has two major functions
Acts as bridge between polymers no
removal is necessary after curing
Acts a solvent/diluent for the resin
Crosslinking agents as solvent
Mobility of resin molecules
Chains get aligned for efficient interactions
Lowers overall viscosity
Enabling complete fiber wet out
Effect of crosslinking agent on
other properties
Curing temperature
Lower the temperature as they add mass to
the system
Shrinkage
Has characteristic exotherm
Has characteristic shrinkage
Shrinkage of polyester: 3%
Shrinkage of Styrene: 17%
Other properties of Styrene
Low cost
Has typical properties characteristic of
Aromatic rings
Stiffness and strength
Low water absorption
Thermal stability
Susceptibility to U.V. light
Brittleness
Other properties of Styrene
As Styrene concentration increases
relative to resin
Properties reach max. value and then
decrease
All crosslinking agents exhibit same behavior:
At different degrees
At different concentrations
Other properties of Styrene
Hazardous material
Strict regulations have established exposure
limits
Methyl Methacrylate (MMA)
Second most important crosslinking agent
Weather and U.V. light resistance
Better smoke rating
Gives off little smoke when it burns
Halogens incorporated in MMA
Improvement in both flame and smoke ratings
Cure control additives
Rate of curing reactions is controlled in
order to
Slow curing:
To increase shelf life
To extend the pot life

Fastcuring: shorten the cure time for high

production rates
To carry out curing at certain temperatures
Inhibitors
Premature free radical generation
Some unsaturation sites may get activated by heat
hot storing conditions
By U.V. light
By contaminants
Avoid premature crosslinking
Extend the shelf life
By deactivating or reacting with free radicals
Several types are available
Most common: free radical scavengers
Inhibitors
Resins should be stored
in cool conditions
In opaque containers
Inhibitors are a must in
hot storing and transportation conditions
Summer production batches may have high
concentration levels of inhibitors
Peroxide should be added accordingly to
Overcome the inhibitor effect
Carry out curing reaction
Promoters/accelerators
Organic peroxides are activated to free radicals by
heating
Promoters/accelerators react with organic peroxides and
split them into free radicals
0.5% by weight of resin
Addition of other metal ions may improve efficiency
Common used are
Cobalt nephthenate
Cobalt octoate
Property optimization
Through optimizing
Viscosity
Curing process
Additives
Optimizing viscosity
Too thick
Poor wet out resin rich and resin poor areas
Trapped air may reduce physical and mechanical properties
Adding thinner/solvent
Allows increasing FVF or filler concentrations
Salts of organic acids
Too thin
Resin may run down without properly wetting or adhering to the
fibers resin poor areas
Adding thixotropes increases viscosities by increasing
hydrogen bonding
Optimizing curing
Gel time and exotherm
measurements
Initial effect of various additives on
curing rate
Optimizing additives
Small proportions (<10%) of
U.V. absorbents
Carbon black
Antioxidants
Pigments and dyes
Molding compounds
Compounder products
Ready-to-use semi prepared products
Limited shelf life
Molding compounds
Sheet molding compounds
Bulk molding compounds
Bulk molding compunds
BMC or DMC
5 cm long fibers+filler+initiator+UP resin
Used for compression molding
Automated and rapid molding of moderately
complex automobile parts
Movement of BMC in the mold may cause
problems
Longest dimension is limited to 40 cm
Sheet molding compound
Ingredients are same as those of BMCs
Fiber lengths can be longer in SMCs
Thickness of sheet: around 0.25 inches
Little movement of material is required in
the mold
SMC process