Professional Documents
Culture Documents
9 - Epoxies
9 - Epoxies
The University of Southern Mississippi Hattiesburg, MS 39406 PSC 470/570, Fall Semester 2006
(O
C CH 3
O CH CH 2
DGEBA Based
Reactions of Epoxides
Acetoacetates
O O O C C
O C C
H O C C CH3 C O O
Acetals
+
OR` R CH OR`
C
O C C OR` R CH OR`
+ H3C C CH2 C OR
Acetylenes
O C C
Acetonitriles
O C C R
+ HC
CR
C C C CR OH
RCH2CN
C C C CN OH H
Acyl Halides
O C C
Acid Anhydrides
O C C O O O O
+ RC Cl
O
Cl
C C O CR O
RC O CR
RC O C C O CR
Handbook of Epoxy Resins, Lee and Neville, McGraw-Hill Book Company, New York, NY, 1967.
Reactions of Epoxides
Alcohols
O C C
+R
OH
RO C C OH
Aldehydes
O C C O
+R C H
BF3
C C
O C O
R H
Amides
O C C H
RC NH2 O
RC N O C C OH C C OH RC N O
Amines - primary
O C C
+ RNH2
HO C C NHR
O C C
+ RC N
O C C OH
C C OH
R HO C C N C C OH
Handbook of Epoxy Resins, Lee and Neville, McGraw-Hill Book Company, New York, NY, 1967.
+ R2NH
HO C C N R
Amines - tertiary
O C C
+ R3N
H2O
HO C C N R R R
OH
NH3
HO C C NH2
O C C
RC OH O
RC O C C OH O
OH C C HO C C N C C OH H HO C C N C C OH
Handbook of Epoxy Resins, Lee and Neville, McGraw-Hill Book Company, New York, NY, 1967.
Phosphoric acid
O C C OH O P O C C OH OH
RC R O
C C
O C O
R
C
O C
H3PO4
O C C
Self - polymerization
O C C CH2 CH2 O CH2 CH2 O CH2 CH2 O n-2
Water
O C C + H2O HO C C OH HO C C O C C OH
Handbook of Epoxy Resins, Lee and Neville, McGraw-Hill Book Company, New York, NY, 1967.
Epoxide Polymers
Polymers in which the epoxide ring plays a part either in polymer synthesis or curing Most of the epoxides are based on the condensation products of bisphenol-A and epichlorohydrin This reaction, known as the Taffy process, is used to produce lower molecular weight epoxides
Driers
Epoxy esters
Aminoplast resins
Baking Finishes
Baking systems
Fatty acids
Maintenance & Marine Coatings High solids maintenance and marine coatings
Epoxide Polymer
Isocyanates
Electrodeposition coatings
Cationic initiators
UV cure coatings UV cure coatings
Acid functional polyester and Decorative powder acrylic resins coatings Acid anhydride Powder coatings for pipe Dicyandiamide
Electrical insulation Decorative powder coatings
Acrylate esters
Acrylic acids
Synthesis of DGEBA
O 2ClCH2CH CH 2 CH 3 + HO C CH 3 OH ClCH2CH CH2 O CH 3 C CH 3 O CH2 OH CHCH2Cl + 2 NaOH OH NaOH
Chlorohydrin intermediate
O H2C CH CH 2 O CH 3 C CH 3 O CH2 O CH CH 2 + 2NaCl + H2O
Epoxide Polymers
O H 2C CH CH 2 CH 3 OH O CH 2 CH CH 2 CH 3
(O
C CH 3
)nO
C CH 3
O CH 2
O CH CH 2
n value
0 -1 1-2 2-4 4-9 9-12
Molecular weight
350-600 600-900 900-1600 1400-2900 2900-3750
E.E.W.
170-310 310-475 475-900 900-1750 1750-3200
Melting Point oC
< 40 40-70 70-100 100-120 130-150
R.A. Pearson, A.F. Yee, Toughening mechanisms in elastomer-modified epoxies, Journal of Materials Science, 2571-2580, 1989.
R.A. Pearson, A.F. Yee, Toughening mechanisms in elastomer-modified epoxies, Journal of Materials Science, 2571-2580, 1989.
O CH 2
O CH CH 2
+
CH 3
+ HO
-
C CH 3
OH
O H 2C CH CH 2
CH 3
OH O CH 2 CH CH 2 O )n
CH 3 C CH 3 O CH 2
(O
C CH 3
O CH CH 2
PhenoxyTM polymers can be crosslinked with amino polymers, phenolics or isocyanates to improve their hardness and resistance to heat and chemicals, but flexibility and impact resistance are adversely affected Isocyanate cured systems have been used for jet fuel tank linings
O H 2C CH CH 2 O CH 2 O CH 2
O CH CH 2
Resole Synthesis
Alkaline conditions:
The reactions possible are a) Methylolation:
OH
OH
OH
CH 2O
OH
+
CH2OH
CH2OH
OH HO CH2 CH2
CH2
OH
CH2
OH
Multi-functional Epoxides
Multi-functional epoxides are used in extreme service condition systems to produce a crosslinked polymers with outstanding chemical resistance. Examples of such epoxides are:
Epoxide novolacs Tetraglycidyl-1,1,2,2-(para-hydroxyphenol) ethane Triglycidyl para-amino phenol Triglycidyl isocyanurate
Tetraglycidyl-1,1,2,2-(parahydroxyphenol) ethane
H2C O CH CH 2 O O CH2 CH CH2 O
CH
CH
O CH2
Multi-functional Epoxides
O
O CH 2 O CH CH 2
O H 2C CH
CH2 N O N
CH 2 O
O CH CH 2
CH2
O H 2C CH N CH2 CH2 O CH CH2
HC O H 2C
Trigylcidyl para-aminophenol
Triglycidyl isocyanurate
Cycloaliphatic Epoxides
Cycloaliphatic epoxides differ from conventional bisphenol-A based epoxides in several ways:
All aliphatic React readily with acids but not with amine/amide type conventional epoxide curing agents Viscosity of 350 cPs Excellent weatherability
Cycloaliphatic Epoxides
O
UVR-6105
O O O
Bis-(3,4-epoxycyclohexyl) adipate
Miscellaneous Epoxides
Polyglycol epoxides
Replacing the bisphenol-A of conventional epoxides by polyoxyalkylene produces epoxides with all aliphatic structures, high flexibility and elongation, but also lower chemical, solvent and heat resistance properties These epoxides are used as modifiers for conventional epoxides at levels up to 30 wt%
O H 2C CH CH 2 O CH 2 R CH O
n
R CH 2 CH O CH 2
O CH CH 2
(CH2)7
CH (CH 2)6 CH 3
O CH 2
Br O H 2C CH CH 2 CH 3 O Br C CH 3
Br OH O CH 2 Br CH CH 2
n
Br CH 3 O Br C CH 3
Br O CH 2 Br O CH CH 2
Amine adducts Aromatic amines Acid anhydrides Acrylics or Polyesters TGIC Amino polymers
RNH 2
CH CH 2 OH
NHR
CH CH 2 O
CH CH 2 OH
Protective Coatings, Clive H. Hare
N CH 2 R
CH OH
100
90 TETA 80
H 2 N CH 2 CH 2 NH CH 2 CH 2 NH CH 2 CH 2 NH 2
13
Substituent Effects on Tertiary Amine Reactivity with DGEBA Amine Gel time, hours Benzyldimethylamine 5.3 Benzyldiethylamine >300 Dimethylethanolamine 4.3 Diethylethanolamine 17.2 Triethylamine 11.2 Tripropylamine 29 Tributylamine 33 Pyridine 54 Handbook of Epoxy Resins, Lee and Neville, McGraw-Hill Book Company, New York, NY, 1967.
CH3
CH3
CH3
CH3
4-Picoline 58
2-Picoline 112
2,6-Lutidine >500
Handbook of Epoxy Resins, Lee and Neville, McGraw-Hill Book Company, New York, NY, 1967.
R1 C O + H 2N R NH 2 R2
H 2O H 2O
R1 C N R N C R2
R1 R2
+ + +
H 2CO3
RNHCOOH O C H
RNH 3O C N R
Amine Adducts
Epoxide-amine Cyanoethylated amine Polyamides Amido-amines Imidazolines Mannich bases Polyoxyalkyl amines
2 H 2N R NH 2
OH
CH 3 C CH 3 O CH 2
OH CH CH 2 NHR NH2
Isophorone diamine
Diamino cyclohexane
H 2C
CH
H 2N
NH
CH 2
CH 2
These are less reactive than amines but have lower vapor pressure and higher equivalent weight which facilitates mixing in convenient volumes These systems possess excellent chemical resistance and color, and cure satisfactorily under damp conditions to give blush-free films
Protective Coatings, Clive H. Hare
NH R NH2 C O (CH2)7 CH HC
R NH 2
O CH (CH2)7 C NH R NH 2
+ 2 H 2N
HC
H 2N R NH 2
CH 3
(CH 2)n
C NH
R NH 2
Viscosity of amido-amines ranges from 2-6 Ps while polyamides have viscosities above 16 Ps Low viscosity and low VOC coatings can thus be formulated using amido-amines Resistance properties of epoxide-amido-amine systems are lower than epoxide-polyamide systems Applications include concrete coatings, floor coatings, and coatings designed for damp substrates
Protective Coatings, Clive H. Hare
O
H2O
+
H 2N (CH 2)2 NH (CH 2)2
- H 2O
NH 2
CH 3
(CH 2)n
C NH
(CH 2)2
NH
(CH 2)2
NH 2
H 2O - H 2O
H 2N R NH 2
CH2NHRNH 2
The functionality of the amine is reduced, but the phenolic hydroxyl acts as a catalyst These systems possess excellent adhesion and chemical resistance and can be applied and cured under damp and cold conditions (~0oC)
Protective Coatings, Clive H. Hare
Polyoxypropylene diamine
H 2N CH CH 2 CH 3
CH 3
CH 3
CH 3 CH 3 C CH 2 (OCH 2CH) NH 2
3
Aliphatic Amines
CH2NH2
CH2NH2
CH2NH2
CH2NH2
m-xylene diamine
Aromatic Amines
Aromatic amines generate crosslinked films with higher rigidity and brittleness due to the increased aromatic content Resistance properties are also enhanced relative to the aliphatic amine cured epoxides All aromatic amines are dark colored, irritating, and toxic by nature Applications include concrete sewer pipe linings, flooring applications and chemical resistant tank linings
NH 2
m-phenylene diamine
O H 2N S O NH 2 H 2N
H 2N CH 2 NH 2
Acid Anhydrides
The reaction of epoxides with anhydrides needs to be either acid or base catalyzed to facilitate the opening of the anhydride In presence of acid catalysts, etherification reaction between epoxide molecules predominates and anhydride levels required drop to 55% of the stoichoiometric level In presence of base catalysts, esterification reaction between the epoxide and anhydride ensues completely and stoichiometric levels of anhydrides are required for full cure
Trimellitic anhydride
O C C O O
Pyromellitic anhydride
O C C O O
Phthalic anhydride
Carboxylated Polymers
Epoxides will react with polymers containing carboxyl groups, such as acrylics and polyesters under base catalyzed conditions Epoxides will also react with the hydroxyl groups in these polymers under acid catalyzed conditions Curing temperatures are high, i.e. 175-200oC
TGIC-Polyester Systems
Epoxide (TGIC)-polyester systems are used extensively in powder coatings
O O H 2C CH CH2 O N N CH 2 CH O CH 2 N CH 2 O O CH CH 2
O C O CH2
OH CH CH2 O N
OH CH CH2
O O C
+
COOH
Polyester
Amino Polymers
Epoxide polymers crosslink with amino polymers mainly through their secondary hydroxyl groups Epoxide-amino polymer systems are widely used in coil coating primers and in beverage can coatings Urea formaldehyde based systems cure faster or at a lower temperature than melamine formaldehyde based systems
Modified Epoxides
Acrylated epoxides Coal tar modified epoxides Epoxide esters Diluents used with epoxides Waterborne epoxides
Acrylated Epoxides
Acrylated epoxides are synthesized by reacting acrylic acid with low molecular weight bisphenol-A epoxides These polymers are used to improve the chemical resistance, hardness and gloss of conventional acrylics Applications include radiation cured coatings, inks, adhesives, and laminates
2 H 2C CH COOH
O H 2C CH C O CH 2
OH CH CH 2 O
CH 3 C CH 3 O CH 2
OH CH CH 2
O O C CH CH 2
RO C CH CH C OH
OH CH CH 2 O
CH 3 C CH 3
O H 2C CH C Cl
OH O CH 2 CH CH 2
RO C CH CH C O CH 2
O C CH CH C OR
O C CH CH 2 O O O CH CH 2 O CH 3 C CH 3 RO C CH CH C O CH 2
O C CH CH 2 O O CH 2 CH CH 2 O O O C CH CH C OR
Epoxide Esters
Oil Types Linseed Oil FA DCO FA Epoxide Ester Properties Fast air drying systems with poor color retention Fast air drying or heat cured systems with good flexibility and chemical resistance Air drying systems with good color and soft flexible films Non air drying systems with very good color, chemical resistance, and flexibility
Soybean FA Coconut FA
H 2C CH O
C O CH 2 O
CH OH
C OH O
CH OH
CH O C O
H2O
During these first two steps, viscosity rise is small corresponding to a large decrease in acid number
H 2C CH O
CH O CH2 CH OH
In order to produce commercially desirable low viscosity, low acid number esters, it is necessary to suppress the etherification while encouraging the esterification steps
Overall properties are inferior to two-pack epoxide polymer films, but their advantages are:
Lower cost Better pigmentation properties Long shelf life
Epoxide-based Diluents
Mono- and di-functional epoxide diluents are employed to reduce the VOC of epoxide based formulations Incorporation of such diluents lowers the hardness, chemical resistance, and heat resistance of coatings while flexibility may be improved due to a lower crosslink density
O H 2C CH CH 2 O CH 2
CH 3 C CH 2 CH 3 O CH 2
O CH CH 2
O CH2
O CH CH2 O CH CH2
CH3
R 2 C C O CH 2 R3
O CH2
Glycidyl neodecanoate
Acrylic Monomers
Acrylic monomers react readily with amines (by Michael addition) and hence when they are incorporated into an epoxide-amine system, they lower the crosslink density of the coating by reducing the amount of amine available for reaction with the epoxides Acrylic monomers are lower in viscosity than low molecular weight epoxides which helps reduce the viscosity of epoxide coatings
Hexanediol diacrylate
C CH2 O C CH CH2
Trimethylolpropane triacrylate
Non-reactive Diluents
Being non-reactive with the epoxides or its cross-linkers, these diluents serve to improve the flexibility of coatings, but solvent resistance, hardness, and heat resistance is lowered Some common examples are:
Coumarone indene copolymers Plasticizers such as butyl benzyl phthalate
2K Epoxy
O H 2C CH CH 2 CH 3 O C CH 3 O CH 2 OH CH CH 2 O CH 3 C CH 3 O CH 2 O CH CH 2
Epoxy Resin
+
Resin
Part A
O C NH R
NH2
or
Resin
Part B
Epoxy Resin
CH 2
CH CH 2
+ H2N
Resin
OH
Epoxy Resin
CH 2
CH CH 2 NH
Resin
2K Epoxy Properties
Toughness Excellent adhesion Commonly used as primers in the general metal industry
Waterborne Epoxides
Performance properties are lower than solventborne epoxides Amine is used as surfactant Epoxide is dispersed with surfactant in water
High concentration of surfactant
Waterborne Epoxides
With all waterborne epoxide systems, viscosity increases are not a very reliable indicator of potlife as the crosslinking reaction takes place within a micelle The gloss of waterborne epoxide systems begins to decrease with time once the crosslinking has proceeded beyond an unacceptable level in the can This can lead to visibly distinct patches of different glosses especially on large architectural areas
+
R NH3
O C R"
Epoxy resin
Low molecular weight Equivalent weight ~190
Epoxy resin
Pre-emulsified using surfactants, shear and/or hydrophilic modification of the epoxy Equivalent weight is >1000
Amine hardener
Mixed with the epoxy to form an emulsion May be salted or used as straight amine
Michael Van De Mark and Kurt A. Kirby, Amer. Paint & Coat. Jour., 81 (15), 20-21, 1997.
H 3C
COOH HC CH
+
HC O C O CH C O
O C C O O
COOH
H 2O
H 3C HC CH HOOC
COOH COOH
+
CH CH 2 O
OH H 2C CH O C O H 3C HC CH COOH COOH
OH CH CH 2 O C O H 3C HC CH COOH COOH
Waterborne Epoxides
Type I
2K - do not require solvents for stability Epoxy is low MW; low equivalent weight Used as concrete and floor coatings Defoamers are important
Type II
1K- need solvents for freezethaw stability Epoxy is higher MW; higher equivalent weight Used for masonry coatings, metal primers, and architectural coatings Longer pot life
Michael Van De Mark and Kurt A. Kirby, Amer. Paint & Coat. Jour., 81 (15), 20-21, 1997.
Primer: two-pack waterborne epoxy Topcoat: two-pack waterborne polyurethane (Hydroxy polyester/acrylic hardened with polyisocyanate)
J. Kruger, Journal of Protective Coatings and Liners, p. 30-38, September, 2000.