PHENOXY RESINS IN EPOXYPOLYAMIDE MAINTENANCE COATINGS

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PHENOXY RESINS IN EPOXY/POLYAMIDE MAINTENANCE
COATINGS

• InChem Corp.
• Rock Hill, SC

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GENERICALLY PHENOXY RESINS ARE THE HIGH
POLYMERS OF DIPHENOLS AND EPICHLOROHYDRINTHE
INDUSTRY STANDARD USES BISPHENOL
APOLY(HYDROXYETHERS)
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PHENOXY RESIN

• THERMOPLASTIC, AMORPHOUS, OPTICALLY CLEAR, RIGID,
  TOUGH
• THERMOSETTABLE WITH CROSSLINKERS
• USED IN
• PLASTICS
• COATINGS
• INKS
• ADHESIVES
• COMPOSITES

DRUM LININGS Zn-RICH CAN COATINGS
COIL WIRE ENAMELS GLASS
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Phenoxy Region
Solid Grade Epoxies
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SOME FORMS OF PHENOXY RESIN
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J
Tg 98oC 9000 psi tensile strength 380,000 psi
modulus 90 elongation at break 410,000 psi
flexural mod.
H
C
Tg 84oC 8662 psi tensile strength 312,000 psi
modulus 91 elongation at break 331,900 psi
flexural mod.
B
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TRANSLATION OF PHENOXY PLASTIC PROPERTIES TO
COATINGS BENEFITS

• 120 Rockwell Hardness
• Tg 84 to 98oC
• Flexural modulus (gt 310,000 psi)
• Tensile strength (9000 psi)
• Elongation at break (90)
• Sol. Parameter of 10.68
• OH functionality gt 40
• Vapor barrier (H2O, O2)
• Aromaticity

• 5H Pencil Hardness
• Stiffener for soft films
• Flexibilizer for brittle films
  a hard plasticizer
• Adhesion promoter compatibility with epoxies
  corrosion resistance

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SOLVENTS and PHENOXY RESINS

• POLAR APROTIC SOLVENTS ARE BEST
• NMP, THF, CYCLOHEXANONE, GLYCOL ETHERS/ESTERS
• MEK IS VERY EFFICIENT, BUT HAS LIMITATIONS
• AROMATICS AND LOW ESTERS ARE DILUENTS
• VOC EXEMPT ACETONE AND METHYL ACETATE ARE USEFUL
  DILUENTS
• STRAIGHT PHENOXY SOLUTIONS OCCUPY THE LOW SOLIDS
  DOMAIN (lt 30 NV for lt 1000 cP)
• BACKBONE MODIFICATION CAN LOWER TG FOR
  SOLIDS/VISCOSITY IMPROVEMENTS (e.g.,
  esterification)

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PHENOXY/EPOXY BLENDS

• COMPATIBLE WITH ALL BISPHENOL A/F TYPE LIQUID
  RESINS
• 10 BY WEIGHT PHENOXY MIXTURES CAN USE REACTIVE
  DILUENTS GLYCIDYL ETHERS, BENZYL ALCOHOL,
  PROPYLENE CARBONATE
• COMPATIBLE WITH ALL SOLID GRADE BISPHENOL A TYPE
  EPOXY RESINS
• 10 TO 25 BY WEIGHT PHENOXY CONTENT CAN BE
  FLAKED ALL HAVE HIGHER SOFTENING POINTS AND MELT
  VISCOSITIES
• COMPATIBLE WITH CYCLOALIPHATIC EPOXY RESINS
• PHENOXY WILL NOT GENERALLY REACT WITH AMINES, BUT
  WILL REACT IN LEWIS ACID AND/OR ANHYDRIDE SYSTEMS
  (through hydroxyl groups)

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2K EPN/AMIDOAMINE PLAQUES IMPACT RESULTS
CONTROL
10 PHENOXY
6 in.-lb. at RT after annealing at 155oC
SHORE D 83 BARCOL 30
SHORE D 82 BARCOL 30
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PHENOXY MODIFIED EPOXY COATINGS (350oF for 15
min.)
LIQUID EPOXY RESIN DETA
20
40
60
CONTROL
PARTS PHENOXY
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PHENOXY RESIN AS MODIFIER FOR 2K EPOXY-POLYAMIDE
PRIMER

• STUDIED 5 AND 10 ADDITIONS OF PHENOXY TO
  STANDARD LIQUID EPOXY RESIN (WPE 190)
• SOLVENT-BORNE SYSTEMS
• MEK, MIBK, XYLENE
• CURED WITH CONVENTIONAL MODIFIED POLYAMIDE
• ANCAMIDE 2050 (Air Products) 1/1 STOICHIOMETRY
• PIGMENTATION (PVC ABOUT 35) INCLUDING
• RED IRON OXIDE
• ZINC PHOSPHATE
• TALC AND BaSO4 EXTENDERS

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PHENOXY RESIN AS MODIFIER FOR 2K EPOXY-POLYAMIDE
PRIMER cont.

• SUBSTRATES INCLUDED
• CRS (IRON PHOSPHATED) GRIT BLASTED HOT ROLLED
  STEEL
• SPRAY APPLICATION at 68 KU
• AIR DRIED 7 DAYS at RT
• TESTS INCLUDED
• PHYSICAL PROPERTIES VISCOSITY, VOCs, VOLUME
  SOLIDS
• DRY TIME, POT LIFE, HARDNESS, GLOSS, ADHESION,
  IMPACT
• CHEMICAL SPOT TESTS (24 hr.), MEK DOUBLE RUBS
• SALT SPRAY, QCT, PROHESION, WATER IMMERSION (RT
  and 180oF)

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2K EPOXY/POLYAMIDE FORMULATIONS INITIAL
VISCOSITIES
10 PHENOXY
CONTROL
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2K EPOXY/POLYAMIDE FORMULATIONS VOCs BEFORE
AFTER REDUCTION
CONTROL
10 PHENOXY
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2K EPOXY/POLYAMIDE FORMULATIONS SPEED OF DRY
CONTROL
10 PHENOXY
POT LIFE 20-24 HR. 36-42 HR.
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2K EPOXY/POLYAMIDE FORMULATIONS PHYSICAL
PROPERTIES
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2K EPOXY/POLYAMIDE FORMULATIONS SPOT TESTS AT 7
DAYS
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2K EPOXY/POLYAMIDE FORMULATIONS SALT
SPRAY/PROHESION (on GBS, 3 mil)
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2K EPOXY/POLYAMIDE FORMULATIONS WATER/HUMIDITY
RESISTANCE
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REVIEW OF 2K EPOXY/POLYAMIDE COATINGS RESULTS

• BENEFITS OF 10 PHENOXY MODIFICATION INCLUDE
• FASTER DRY TIMES
• LONGER POTLIFE
• IMPROVED CHEMICAL RESISTANCE TO WATER, AND NITRIC
  ACID
• READ FULL TECHNICAL PAPER FOR MORE DETAILS
• SEE COMPELLING STORY BROCHURE FOR HIGHLIGHTS
• NEW WORK TO ADDRESS
• USE OF EXEMPT SOLVENTS TO LOWER VOC
• REPEAT CORROSION/WATER TESTING WITH APPROPRIATE
  EXTERIOR TOPCOAT

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PHENOXY POLYMER STRUCTURE
Condensation Polymer of
Bisphenol A and Epichlorohydrin
OH
HO
n
m
n m is gt 40
Graft Caprolactone Monomer onto Pendant Backbone
Hydroxyls

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PHENOXY POLYMER STRUCTURE
Phenoxy with e-Caprolactone Side Chain
Grafting
OH
HO
n
m
n m is gt 40
O
If n is large, then x will be small, and vice
versa
x

OH
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CAPROLACTONE MODIFIED PHENOXY

Standard Phenoxy Resin Model with Backbone
Hydroxyls
2o hydroxyl
Phenoxy Resin Model with Caprolactone Grafting
1o hydroxyl
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PROPERTIES of CAPROLACTONE GRAFTED PHENOXY RESINS

• 33 GRAFTING
• Tg of 2oC
• primary OH of 50 - 55
• total OH of 130 - 135
• Mw 42,000 daltons

• 20 GRAFTING
• Tg of 30oC
• primary OH of 36 - 40
• total OH of 155 - 160
• Mw 39,000 daltons

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EXPECTED BENEFITS OF CAPROLACTONE-MODIFIED
PHENOXY TO EPOXY FORMULATIONS

• IMPROVED VOCS
• FASTER REACTION IN UV CATIONIC CURE
• PRIMARY HYDROXYL CONTENT
• MOBILITY OF GRAFTED SIDE CHAINS
• IMPROVED FLEXIBILITY
• HIGHER LOADING OF PHENOXY
• INHERENT LOWER MODULUS