Epoxy Chemistry

Overview

Structure and reactivity

– Epoxy resin chemistry
– Amine crosslinking reagents
Epoxy end use and application
Formulation strategies
Future work
Epoxy resins: diglycidyl ether of
bisphenol-a (DGEBA)
Solid epoxy resin
Diglycidyl ether of Bisphenol-F
Epoxy novolac resins
Epoxy resin properties
Cycloaliphatic epoxy resin

Prepared by peroxidation of cyclohexenes

Different reactivity
Much better UV durability
 aliphatic epoxy resin
Co polymers of glycidyl methacrylate

Exterior durability
Used in some automotive topcoats
The epoxide ring
Epoxide bonding
 Epoxy diluents

Used mainly to lower the viscosity of the

epoxy resin, or the system as a whole
Can also impart flexibility
Classified as either reactive, or non-
reactive
– Non reactive towards amine, epoxy, or
hydroxyl groups.
Use carefully, can negatively impact
cross link density of system
 Non reactive diluents
Phthalates

dimethyl dibutyl

Butyl benzyl phthalate

 Non reactive diluents

Phenols, e.g. nonylphenol

Alcohols
• Benzyl, also accelerator for amine cure
• Furfuryl alcohol
• Butanol
Solvents such as xylene, or high-
flash naptha
– Use at 2-3 phr for minimal effect on cure
properties
 Reactive diluents

Butyl glycidyl ether

– Gives greatest viscosity reduction.
Cresyl glycidyl ether
Alkyl glycidyl ether/aliphatic glycidyl
ether
– Used where low volatility levels required.
Epoxidized vegetable oils or esters
– React into system giving internal plasticizer
effect.
 Crosslinking reagents for
epoxies
Primary and secondary amines
Tertiary amine catalyzed
homopolymerization
Mercaptans
Phenols
Carboxylic acids/anhydrides (heat cure)
Amino resins (melamines etc.) and
isocyanates
– React with OH groups, heat cure
 Amine cross linked epoxies
Coatings, adhesives, civil engineering,
and composites
Excellent coatings characteristics
– Corrosion resistance
– Solvent resistance
– Good physical properties
– Ambient cure, as low as 5°C (with proper
curative).
Biggest limitation: exterior durability
Amine crosslinking
mechanism
Polyethyleneamines
 Polyethyleneamines
Pros Cons
High reactivity Poor compatibility
High chemical resistance Difficult to handle
High strength Poor mix ratios
High crosslink density Incomplete reaction

Little use in coatings unless modified.

 Polyetheramines

Several molecular weights, about 230-2000

Monoamines and triamines also
Cycloaliphatic amines

Ring structures boost Tg

Ability to vitrify requires correct formulation
 Aromatic amines

Declining market due to carcinogenicity

concerns
Used in powder coatings, some flooring
systems
Polyamides
 Polyamides
Pros Cons
Good flexibility Moderately high viscosity
Very hydrophobic Moderate incompatibility
Excellent corrosion Induction time required
resistance Generally poor at low
Low cost temperature
Good handling Modest chemical
resistance
 Amidoamines
Tall oil fatty acid + polyethyleneamine (usually TEPA)

Pros Cons
Low viscosity Brittle
Low cost Incompatibility/blush
Easy handling Poor appearance
Very good corrosion
resistance
Amine Adducts
 Mannich Bases

Pros: Cons:
Fast cure High color
Low temperature cure Residual phenols:
labeling concern
Tertiary amines: catalysts

Homopolymerization
Also proton (acid catalyzed)
Sole curing mechanism at high temperatures
Co-curing mechanism at ambient
Tertiary amines cont.

Tertiary amino phenols

Suitable for acceleration
Optimize at lowest level
Yellowing
Poorer weathering
Unreacted amine
 Incompatibility effects
Graininess, “blush,” exudate
Amines at surface can react with
moisture in air, or CO2

Solutions:
– More compatible amine and epoxy
– Compatibilizing agents in formula
– Induction time
– Higher temperature, lower RH application
 Why Use Epoxies?

Advantages Disadvantages
– Chemical resistance – Chalking
– Adhesion – Poor gloss retention
– Corrosion resistance – Lifts old film
– Tough, hard film – Often 2K systems
– Moderately flexible (potlife)
 Many applications
Marine and maintenance
Transportation: ship, rail, air
Civil engineering, flooring etc.
Asset protection
– Protection from corrosion
– Protection from chemical attack
Improve substrate properties
– Reduce porosity of concrete
– Improve cleanability
Epoxy lining being applied to ballast tank of
US Navy research vessel
Epoxy lining being applied to ballast tank of
US Navy research vessel
Glass flake filled epoxy coating being
applied to US Army Corps of Engineers
barge
Epoxy deck coating, USS Midway, San
Diego
Tank car coated with fast dry epoxy topcoat
Epoxy coating system for steel
Epoxy vs. alternative resins
 Formulation basics

Solvent-free, 100% solids.

– Low VOC achievable
– Improved cross link density
– Specialized equipment often needed to
apply (plural spray).
Solvent borne
– More surface tolerant
– Easier to use
– More flexible
Formulation basics cont.
 Stoichiometry

Epoxy: Epoxide equivalent weight, EEW

Amine: Amine hydrogen equivalent
weight, AHEW
 Stoichiometry

Example:
– 100 g of bis-a epoxy with an EEW of 193.
• Therefore, 100g/193 = 0.518 equivalents
– 100 g of amine curing agent with AHEW
110
• 100/110 = 0.90 equivalents.
*Need to mix 57 g of curing agent with 100 g
of epoxy for 1:1 stoichiometry.
 Stoichiometry
Adjust stoichiometry for specific properties
 Formulation properties

Epoxy Strengths:
– Tenacious adhesion to most substrates
– Barrier properties
– High chemical, corrosion resistance
Tailor properties to application
– Epoxy resin selection
– Curing agent selection
– Stoichiometry, PVC, VOC
 Formulation properties

Weaknesses
– Exterior durability
System can be highly formulated to
resist weathering, but cost becomes a
factor
– Polysiloxane chemistries
– Cycloaliphatic epoxy systems
– Other “urethane-like” technologies
 Future developments

Rapid cure, return to service

Low temperature cure systems
High temp, high pressure linings
Alloy replacement
 Summary

Epoxy resin and amine crosslinking

reagents
Epoxy end use and application
Formulation strategies
Future developments and industry
trends.