Epoxide Polymers in Coatings

The University of Southern Mississippi Hattiesburg, MS 39406 PSC 470/570, Fall Semester 2006

Outline for Epoxy Polymers

I. Basic Synthesis II. Reactions of Epoxides III. Types of epoxy resins A. BPA & BPF epoxides B. Multifunctional epoxides C. Miscellaneous epoxides D. Cycloaliphatic epoxides IV. Epoxide curing agents A. Amines B. Aliphatic amines C. Aliphatic amine adducts D. Aromatic amines E. Acid anhydrides F. Carboxylated polymers V. Modified epoxides A. Acrylated epoxides B. Coal Tar modified epoxides C. Epoxide esters D. TGIC-Polyester E. Amino epoxides VI. Diluents A. Epoxide based diluents B. Acrylic monomers C. Non-reactive diluents VII. Waterborne epoxides

Typical Epoxide Polymer

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

DGEBA Based

Typical Characteristics of Epoxide Polymers

Chemical and heat resistance Adhesion Low shrinkage Ease of fabrication Toughness Flexibility Abrasion resistance Superior elevated temperature performance

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.

Reactions of Epoxides (continued)

Amines - secondary
O C C R

+ R2NH

HO C C N R

Amines - tertiary
O C C

+ R3N

H2O

HO C C N R R R

OH

Ammonia Carboxylic acids

O C C

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.

Reactions of Epoxides (cont.)

Ketones
O C C

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

Protective Coatings, Clive H. Hare

Epoxide Polymers in Coating Science

Ambient-Cure Coatings
Air drying esters

Driers

Epoxy esters

Aminoplast resins

Baking Finishes
Baking systems

Fatty acids
Maintenance & Marine Coatings High solids maintenance and marine coatings

Aminoplast and Industrial baking finishes phenoplast resins

Container coatings

Polyamides, amine adducts Ketoimine amidoamines

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

Free radical initiators

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

Diglycidyl ether of bisphenol A (DGEBA)

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

Epoxide Polymers (contd)

Pure DGEBA is not available commercially as it tends to crystallize easily Low molecular weight epoxides are a polydisperse mix of epoxides with n values between 0 and 1 and have an average molecular weight of 350-600 The higher molecular weight epoxides are synthesized by the fusion or advancement process using benzyl trimethylammonium hydroxide as a catalyst

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.

Fusion aka Advancement Process

O H 2C CH CH 2 O CH 3 C CH 3
CH 2 N(CH3)3 OH

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

Fusion Process (cont.)

Commercial bisphenol-A contains mono- and trifunctional byproducts which interfere with the linear structure of epoxide polymers Hence, the Fusion process is preferred for preparing very high molecular weight epoxides due to the reduced likelihood of chain branching and unwanted increase in melting point and viscosity

Classes of Epoxide Resins

Low molecular weight Medium molecular weight High molecular weight Very high molecular weight

Low Molecular Weight Liquid Epoxides

Liquid epoxides (n<1) are important in formulating zero and low VOC coatings for high performance applications Two-pack systems with VOCs below 250 g/L (2.1 lb/gal) are commercially available Cross-linkers with high equivalent weights such as amidoamines, polyamides, and polyglycol diamines are preferred to provide for flexibility

Medium Molecular Weight Epoxides

Medium molecular weight epoxides (n=2) are widely used as binders for two-pack amine and amide cured coatings These polymers are normally available as 75% solutions in aromatic or ketone solvents with viscosities between 20-100 Poise Amide cured epoxide coatings provide the best balance of properties with very good chemical resistance, hardness, flexibility, and adhesion

Medium Molecular Weight Epoxides (cont.)

Pot lives varies from 1 hour to 24 hours depending on curing agents employed but dry-to-touch times are typically 4-8 hours. Full cure may take up to 10 days for polyamide cured epoxide coatings Applications include maintenance coatings for offshore oil rigs, bridges, aircraft primers, interior coatings for water and sewage treatment, concrete floor coatings, and swimming pool coatings

High Molecular Weight Epoxides

High molecular weight epoxides (n=4) are used in the manufacture of epoxide esters Epoxide esters are widely used in metal primers for appliances and automobiles and clear finishes for concrete floors Linseed oil, DCO, and tall oil fatty acids are used in airdrying epoxide ester synthesis while coconut oil fatty acids are used for heat-curing epoxide esters

High Molecular Weight Epoxides (cont.)

Epoxide esters are also classified according to their oil content as long, medium, and short oil epoxide esters like oil-modified polyesters 0.3-0.9 equivalents of acid per oxirane are used This corresponds to 55-65% fatty acid modification for long oil esters and 30-45% fatty acid modification for short oil esters

High Molecular Weight Epoxides (cont.)

Epoxides with n = 4 are also used in dicyandiamidecured powder coatings, cathodic electrodeposition coatings, and in metal primers Epoxides of n = 7 to 9 with high hydroxyl contents are used as co-reactants with:
Amino polymers Phenolic polymers in high temperature curing wire enamels, coil coatings, can coatings, and drum coatings Powder coating polymers for high build applications (>15 mils)

Very High Molecular Weight Epoxides

Phenoxy polymers have very high melting points, produce very high viscosity solutions, and do not require curing agents to form useful films They are sold either as solids or as dilute solutions (35% solids) in MEK or cellosolve acetate Thermoplastic coatings based on these polymers have good flexibility, impact and abrasion resistance, chemical resistance and excellent adhesion, but poor resistance to solvents from which they are cast

Very High Molecular Weight Epoxides (cont.)

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

Other Epoxide Polymers

Bisphenol F based Multifunctional Cycloaliphatic Miscellaneous

Bisphenol F Epoxide Polymers

O H 2C CH CH 2 O CH 2 O CH 2

O CH CH 2

Bisphenol F Epoxide Polymers

The isopropylidene linkage and presence of only para-para isomer confer rigidity to bisphenol-A polymers. Bisphenol-F has ortho-ortho, ortho-para, and parapara isomers along with a methylene linkage which produces more flexible polymers. The presence of isomers in bisphenol-F also reduces the crystallization tendency and produces polymers with a lower viscosity than bisphenol-A.

Resole Synthesis
Alkaline conditions:
The reactions possible are a) Methylolation:
OH

OH

OH

CH 2O

OH

+
CH2OH

CH2OH

OH HO CH2 CH2

Di- and tri-methylol phenols are also produced

OH OH CH2 OH
HO CH 2 OH CH 2 OH

CH2

OH

CH2

OH

2,6 di-methylol phenol

2,4,6 tri-methylol phenol

2,4 di-methylol phenol

Bisphenol F Epoxide Resins (contd)

The greater mobility of bisphenol-F facilitates a higher degree of crosslinking than bisphenol-A polymers of similar molecular weight leading to a higher Tg, and better solvent and chemical resistance The lower viscosity facilitates formulating of low VOC coatings with a high degree of chemical resistance Bisphenol-F epoxide coatings are replacing bisphenolA epoxide coatings in many applications

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 H2C CH CH2 O O CH2 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

3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate UVR-6128

O O O 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

Miscellaneous Epoxides (cont.)

Cardanol based epoxides
Cardanol (3-n-pentadecenyl phenol) is a major constituent of cashew nut shell liquid (CNSL) Epoxidation is introduced via the phenolic hydroxyl or the unsaturation on the aliphatic chain
O CH 2 O CH CH2 O CH CH 2

(CH2)7

CH (CH 2)6 CH 3

O CH 2

Miscellaneous Epoxides (cont.)

Brominated epoxides
Brominated epoxides are used specifically in fireretardant applications Various levels of halogen substitution are feasible

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

Epoxide Curing Agents

Amines
Ketimines

Amine adducts Aromatic amines Acid anhydrides Acrylics or Polyesters TGIC Amino polymers

Amine Curing Agents

Primary and secondary amines are the most widely used curing agents for epoxides Amine cured systems are employed as two-pack, ambient-cured coatings The molecular weight of the amine, its nature, i.e., aliphatic/aromatic, primary/secondary/tertiary, controls the reaction rate and physical/chemical properties of the finished film

Protective Coatings, Clive H. Hare

Amine Curing Agents (cont.)

CH CH 2 O

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

Amine Curing Agents (cont.)

Unmodified alkylene amines such as diethylene triamine (DETA), triethylene tetramine (TETA), and tetraethylene pentamine (TEPA) were among the first amines used as curing agents These amines cure exothermically and generate highly crosslinked films with excellent resistance properties but low flexibility These amines have high vapor pressures and are skin sensitizers and respiratory irritants
Protective Coatings, Clive H. Hare

Effect of Curing Agent Concentration on Epoxide Properties

120
H 2 N CH 2 CH 2 NH CH 2 CH 2 NH 2

DETA Deflection temperature, oC 110 5

100

90 TETA 80
H 2 N CH 2 CH 2 NH CH 2 CH 2 NH CH 2 CH 2 NH 2

11 12 10 phr of curing agent with DGEBA

13

Handbook of Epoxy Resins by Lee H. and Neville K.

Amine Curing Agents (Cont.)

Phenolic tertiary amines e.g. tris(dimethylaminomethyl) phenol, p-toluenesulfonic acid, salicylic acid and hydrogen bond donors such as phenol, alkyl phenols serve as catalysts for the epoxide-amine reaction Hydrogen bond acceptors such as ethers, esters, and nitro groups act as retarders for this system Ketones, especially acetone and MEK, form ketimines with amines and hence act as retarders
Protective Coatings, Clive H. Hare

Epoxide Reactivity Data

Reactivity of DGEBA vs. Basicity of Tertiary Amine Amine Ionization constant (hours) Benzyldimethylamine Benzyldiethylamine Triethylamine Tripropylamine Pyridine 8.5 x 10-6 3.6 x 10-5 6.4 x 10-4 5.5 x 10-4 2.3 x 10-9 Gel time 5.3 >300 11.2 29 54

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.

Epoxide Reactivity Data (cont.)

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.

Aliphatic Amine Adducts (cont.)

Ketimines
Ketimine blocking has become important in the formulation of two-pack, high solids systems where the maintenance of low application viscosities are critical

R1 C O + H 2N R NH 2 R2

H 2O H 2O

R1 C N R N C R2

R1 R2

Protective Coatings, Clive H. Hare

Amine Curing Agents (cont.)

Unmodified amines react rapidly with atmospheric carbon dioxide and moisture to form carbamates that produce blushing on the film surface, especially at low temperatures and high humidities
H 2O H 2CO3
RNHCOOH

+ + +

CO2 RNH 2 RNH 2

H 2CO3
RNHCOOH O C H

RNH 3O C N R

Protective Coatings, Clive H. Hare

Amine Curing Agents (cont.)

Amine induced blushing may be reduced by allowing an induction period after mixing the two components just before application

Protective Coatings, Clive H. Hare

Amine Adducts
Epoxide-amine Cyanoethylated amine Polyamides Amido-amines Imidazolines Mannich bases Polyoxyalkyl amines

Aliphatic Amine Adducts

Epoxide amine adducts
O H 2C CH CH 2 O CH 3 C CH 3 O CH 2 O CH CH 2

2 H 2N R NH 2

OH

CH 3 C CH 3 O CH 2

OH CH CH 2 NHR NH2

H2N RNH CH 2 CH CH2 O

Protective Coatings, Clive H. Hare

Aliphatic Amine Adducts (cont.)

Cycloaliphatic amines
Isophorone diamine, diamino cyclohexane, and 4,4-bis(pamino cyclohexyl) methane are the commonly used cycloaliphatic amines with epoxides
H 3C H 3C H 3C CH 2NH2 NH2 NH2 NH2
H 2N CH 2 NH 2

Isophorone diamine

Diamino cyclohexane

4,4-bis(p-amino cyclohexyl) methane

Protective Coatings, Clive H. Hare

Aliphatic Amine Adducts (cont.)

Cyanoethylated amines
H 2N R NH 2

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

Aliphatic Amine Adducts (cont.)

Polyamides
Long chain fatty acid dimers derived from vegetable oils are reacted with slight excess of primary amines to synthesize polyamides
OH C O (CH2)7 CH HC HC CH (CH2)7 CH CH CH (CH2)5 CH CH3 (CH2)5 CH3 O C OH

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

CH CH CH (CH2)5 CH CH3 (CH2)5 CH3

Protective Coatings, Clive H. Hare

Aliphatic Amine Adducts (cont.)

Polyamide-epoxide systems are the workhorse of high performance protective coatings Increased distance between crosslinking sites produces films that are more flexible and impact resistant than films cured with amines Resistance to chemicals and solvents are lowered though water resistance and corrosion protection are enhanced The higher molecular weight of polyamides also facilitates mixing in convenient ratios An induction period is necessary after mixing and before application
Protective Coatings, Clive H. Hare

Aliphatic Amine Adducts (cont.)

Amido-amines
Amido-amines are condensation products of an amine and a monofunctional fatty acid
O
CH 3 (CH 2)n COOH

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

Aliphatic Amine Adducts (cont.)

Imidazolines
Imidazolines are the condensation products of amines and monofunctional acids reacted at high temperatures
CH 3 (CH 2)n COOH

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

N CH2 CH3 (CH2)n C N CH2 (CH2)2 NH2

Protective Coatings, Clive H. Hare

Aliphatic Amine Adducts (cont.)

Imidazoline formation is accompanied by loss of the reactive amine functionality Imidazolines are utilized in low VOC formulations due to their low viscosity, good compatibility with epoxides, and high equivalent weights Like amido-amines, imidazolines have reduced reactivity, reduced cross link density and lower resistance properties Imidazolines are also used to extend the pot life of aliphatic and cycloaliphatic amine catalyzed epoxide systems

Protective Coatings, Clive H. Hare

Aliphatic Amine Adducts (cont.)

Mannich bases
Aliphatic and cycloaliphatic amines are reacted with methylol phenols to yield Mannich bases
OH CH2OH OH

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

Aliphatic Amine Adducts (cont.)

Unmodified cycloaliphatic amines require high temperatures for reaction with epoxides Modification involves use of acid accelerators such as salicylic acid (dissolved in benzyl alcohol) Use of cycloaliphatic amines improves color retention on exterior exposure These systems cure well in cold and damp conditions and exhibit good adhesion to damp surfaces
Protective Coatings, Clive H. Hare

Aliphatic Amine Adducts (cont.)

Polyoxylalkylene amines
Polyoxyethylene and polyoxypropylene amines are primary amine derivatives of polyethylene and polypropylene glycol These amines react slowly and contribute considerable flexibility to the crosslinked film The oxyalkylene structures provide considerable water sensitivity leading to inferior water and corrosion resistance These amines are mostly employed as flexibilizing agents in conjunction with other curing agents

Protective Coatings, Clive H. Hare

Aliphatic Amine Adducts (cont.)

H 2N CH CH 2 CH 3 (OCH 2CH)n NH 2 CH 3

Polyoxypropylene diamine

H 2N CH CH 2 CH 3

(OCH 2CH)n (OCH 2CH 2) (OCH 2CH)l NH 2

m

CH 3

CH 3

Diamine of mixed polyalkylene glycols

CH 3 CH 3 C CH 2 (OCH 2CH) NH 2
3

Polyoxyalkylene triamine based on trimethylol propane

Protective Coatings, Clive H. Hare

Aliphatic Amines

CH2NH2

CH2NH2

CH2NH2

CH2NH2

m-xylene diamine

1,3 - bis (aminomethyl) cyclohexane

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

Aromatic Amines (cont.)

NH 2
H 2N CH 2 NH 2

NH 2

m-phenylene diamine

4,4 - methylene dianiline

O H 2N S O NH 2 H 2N

H 2N CH 2 NH 2

Diamino diphenyl sulfone

2,4 -bis (para-aminobenzoaniline)

Aromatic Amines (cont.)

Some aryl diamines have amine groups removed from the ring by a methylene bridge The methylene group enhances the reactivity of this class of amines providing rapid cure at ambient and sub-ambient temperatures Hard, high gloss finishes are obtained with excellent chemical, water, and solvent resistance These amines are also lighter in color and are less toxic than aromatic amines

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

Acid Anhydrides (cont.)

Curing temperatures are high, 1-2 hours at 200oC, as most anhydrides are solids and need to be melted Anhydride cured systems have lower chemical resistance than the amine cured systems, but are less toxic, cure with lower exotherm, and have longer pot lives These systems are used in casting and laminating applications, and in powder coatings

Acid Anhydrides (cont.)

O HOOC C C O O O O C C O O C C O O

Trimellitic anhydride
O C C O O

Pyromellitic anhydride
O C C O O

Phthalic anhydride

Hexahydro 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

O N CH2 N CH2 CH OH CH2 O C O O

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

Acrylated Epoxides (cont.)

O H 2C CH CH 2 O CH 3 C CH 3 O CH 2 O CH CH 2

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

Difunctional acrylated epoxide

Acrylated Epoxides (cont.)

O H 2C CH CH 2 O CH 3 C CH 3 O CH 2 O CH CH 2
O O

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

Tetrafunctional acrylated epoxide

Coal Tar Modified Epoxides

Refined coal tar pitch is blended with epoxide-amine systems at levels of 1.5-3 times coal tar to epoxideamine solids While the exact mechanism occurring in the reaction is not clear, it has been proposed that the phenolic components of coal tar pitch react with the epoxides and also catalyze the epoxide-amine reaction

Coal Tar Modified Epoxides (cont.)

Medium hard grade coal tar pitches are preferred for use with epoxide systems for best chemical resistance At higher levels of coal tar, resistance to water, corrosion and dilute acids improves At lower levels of coal tar, hardness and resistance to solvent and alkalis improves

Coal Tar Modified Epoxides (cont.)

A disadvantage of these systems are their poor color and poor resistance to UV light Being highly cohesive in nature, these systems require blast cleaned surfaces with a high surface profile for good adhesion Coal tar epoxide systems have been used very effectively in buried, immersed, hidden, and similar difficult-to-access areas providing long-term service without much maintenance

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

Epoxide Esters (cont.)

With increasing fatty acid content:
Chemical resistance Film hardness Drying time Adhesion Gloss retention Cost Viscosity Flow Solubility in aliphatic hydrocarbon solvents Water resistance Flexibility Pigment wetting Exterior durability Color retention

Epoxide Esters (cont.)

Esterification
C OH O
+

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

Epoxide Esters (cont.)

Etherification
CH OH
+

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

Epoxide Esters (cont.)

They are similar to polyester polymers, yet they offer some superior film properties:
Adhesion Flexibility Chemical resistance

Overall properties are inferior to two-pack epoxide polymer films, but their advantages are:
Lower cost Better pigmentation properties Long shelf life

Applications of Epoxide Esters

Automotive primers Appliance primers Flexible tube coatings Drum linings Marine finishes Floor sealers and top coats Metal decorating lacquers Enamels for hardware and metal furniture Industrial maintenance primers and topcoats

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

Epoxide-based Diluents (contd)

H 9C 4 O CH 2 O CH CH 2

O H 2C CH CH 2 O CH 2

CH 3 C CH 2 CH 3 O CH 2

O CH CH 2

Butyl glycidyl ether

O CH2 O CH CH2
R1 O

Diglycidyl ether of neopentyl glycol

O CH CH 2

O CH2

O CH CH2 O CH CH2

CH3

R 2 C C O CH 2 R3

O CH2

Cresyl glycidyl ether

Glycidyl neodecanoate

Diglycidyl ether of resorcinol

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

Acrylic Monomers (contd)

O H 2C CH C O (CH 2)6 O O C CH CH 2

Hexanediol diacrylate

O O C CH CH2 CH2 CH3 CH2 CH2 O C CH O CH2 O

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

Non-reactive Diluents (contd)

O C OC 4H 9 C OCH2C6H 5 O

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

Hardener is typically a polyamine or polyamide

O

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

Waterborne Epoxides (cont.)

Advantages No organic solvents Easy equipment cleaning Excellent adhesion Excellent interlayer adhesion Coating of plastics possible Disadvantages Short pot life Gloss stability Water evaporates slowly Lower chemical resist Wastewater treatment Flash rust

Waterborne Epoxides: Type I

Liquid epoxy resin Part A Mixing just prior to use

Amine curing agent

+
R NH3

O C R"

Part B Amine hardener emulsifies epoxy resin

Epoxy resin
Low molecular weight Equivalent weight ~190

Amine curing agent

Polyamines Salt is formed by reacting with acid
Increased ability to form micelles

Waterborne Epoxides (cont.)

With liquid epoxides (EEW ~ 190):
The curing agents - polyamines or polyamides are neutralized to form quarternary ammonium salts which can emulsify epoxide polymers when the two components are mixed together Cosolvents, non-ionic surfactants, defoamers/antifoaming agents constitute the rest of the formulation Waterborne epoxides based on liquid epoxides are generally used as concrete and floor coatings because of their ability to cure on damp concrete
Ref: Van de Mark M., et al, APCJ, Jan 15, 1997

Waterborne Epoxides: Type II

Emulsified epoxy resin
Aqueous phase amine

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.

Waterborne Epoxides (cont.)

Epoxides of medium molecular weight (n ~ 2) have been rendered water soluble by reacting with hydrated maleinized fatty acids
H 3C COOH

H 3C

COOH HC CH

+
HC O C O CH C O

O C C O O

JOCCA, Novakov P. et al, 1993 (3) pp 111-115

Waterborne Epoxides (cont.)

H 3C HC CH O C C O O
H 2C CH 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

JOCCA, Novakov P. et al, 1993 (3) pp 111-115

Waterborne Epoxides (cont.)

The modified epoxide is then dissolved in water along with a neutralizing agent such as triethylamine Cosolvents are also added to provide better film coalescence These modified epoxides have been found to be suitable for electro deposition and dipping applications

JOCCA, Novakov P. et al, 1993 (3) pp 111-115

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.

Development and Use of Waterborne Coatings for Rail Vehicles in Germany

Maintenance coatings for passenger cars, rail cars, and locomotives is being done exclusively with waterborne coatings:

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.

Development and Use of Waterborne Coatings for Rail Vehicles in Germany

New locomotives, rail cars, and passenger cars are currently coated with solventborne coatings. Next year waterborne coatings will be used for all new rail vehicles. Primer: two-pack WB epoxy or PU Intermediate: two-pack WB epoxy or PU Topcoat: two-pack WB aliphatic PU Anti-graffiti: solventborne clearcoat
J. Kruger, Journal of Protective Coatings and Liners,p. 30-38, September, 2000.