Evaluating the Use of Accelerators in

Phenalkamines for Improving the Low

Temperature Cure PropertiesDr. Frank Cheng

Royce International

HOW LOW CAN WE GO?

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Phenols: Accelerator for Epoxy – Amine SystemMechanism:

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Tertiary Amine: Accelerator for Epoxy – Amine System Mechanism:

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Tertiary Amines: Reactivity with DGEBA**Barusch & Payne, J. Am. Chem. Soc. 65:2196 (1943)

Amine Ionization Constant, Kb

Geltime, hrs25°C

Triethylamine 6.4 X 10(-4) 11.2

Tripropylamine 5.5 x 10(-4) 29

Benzyldiethylamine

3.6 x 10(-5) >300

Benzyldimethylamine

(BDMA)

8.5 x 10(-6) 5.3

Pyridine 2.3 x 10(-9) 54

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DMP: (Dimethylaminomethyl)phenolas AcceleratorBDMA, DMP-10 and DMP-30

BDMA DMP - 10 DMP - 30

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Mannich Reaction and Mannich BaseMannich Reaction: (amino-alkylation of acidic proton named after chemist Carl Mannich )

Mannich Bases: ( for Example: I & II )

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Phenalkamines

Phenalkamines: Based on CNSL

Mannich Base based on Phenols: Phenol, Cresol, tButylphenol, Nonylphenol etc….

Drawback: Solid at RT (liquid product may contain more than 30% of free phenol).

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( R = C15H27 )

MW = 300

Fast Curing: Especially at low temperature (i.e. 5°C & 0°C) 25°C: Full Cure: ~ 9 - 12 hrs 5°C: Full Cure: ~17 - 22 hrs 0°C: Full Cure: ~30 - 40 hrs

Excellent Cure under Damp Conditions Good for Marine and Maintainence Coatings.

Low Blushing

Low Color / Low Viscosity products are available Good for Flooring Applications

Advantage of Phenalkamines as Hardeners for Epoxy

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Reactivity Study - GelationTechne Gelation Timer” 100gram scale 1) Epoxy Resin: DGEBA (BLR: Basic Liquid Resin based on BisphenolA) WPE: 190 (RoyOxy RA-928)

2)Phenalkamines: RoyOxy RA-951, RoyOxy RA-950 RoyOxy RA-593)Accelerators: a) Nonylphenol : M.W. : 220 (RoyOxy RA-444) b) DMP-30: : M.W. : 265 (RoyOxy RA-3054) c) OTBP:2-tert-butylphenol: M.W. : 150 d) CNSL: Cashew Nut Shell Liquid: M.W. : 300

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Phenalkamines selected in this Study

I) EDA Phenalkamine: i.e. RoyOxy™ RA-951 Fast Cure, Low Blushing, Excellent

Corrosion Resistance, High ViscosityII) DETA Phenalkamine: i.e. RoyOxy™ RA-950 Fast Cure, Low Viscosity, Some

BlushingIII) Mixed (EDA/DETA) Phenalkamine: i.e. RoyOxy™ RA-59, RoyOxy™ RA-59

LC Low Viscosity, Low Blushing,

Excellent for Flooring Application ROYCE INTERNATIONAL

Geltime Study @ 25°C

EDA Phenalkamine A.N. : 316 mgKOH/g(RoyOxy™ RA-951) AHEW : 130 Vis. @25°C : 27,200 cP Geltime : (45g/55g BLR) 71 min.

NonylphenolMW: 220

DMP-30MW: 265

2.0% (0.9 g)65.1 min.

2.4% (1.08 g)69.0 min

4.0% (1.8 g)57.5 min.

4.8% (2.16 g)63.6 min.

8.0% (3.6 g)46.5 min.

9.6% (4.32 g)57.1 min.

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Geltime Study @ 25°C

EDA Phenalkamine A.N. : 316 mgKOH/g(RoyOxy™ RA-951) AHEW : 130 Vis. @25°C : 27,200 cP Geltime : (45g/55g BLR) 71 min.NonylphenolMW: 220

DMP-30MW: 265

OTBPMW: 150

CNSLMW: 300

2.0% (0.9 g)65.1 min.

2.4% (1.08 g)

69.0 min.

1.36% (0.61 g)

62.1 min.

2.72% (1.22 g)

66.3 min.

4.0% (1.8 g)57.5 min.

4.8% (2.16 g)

63.6 min.

2.72% (1.22 g)

56.2 min.

5.44% (2.44 g)

55.2 min.

8.0% (3.6 g)46.5 min.

9.6% (4.32 g)

57.1 min.

5.44% (2.44 g)

45.6 min.

10.9% (4.88 g)

46.8 min.

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Geltime Study @ 5°C

EDA Phenalkamine A.N. : 316 mgKOH/g(RoyOxy™ RA-951) AHEW : 130 Vis. @25°C : 27,200 cP Geltime : (45g/55g BLR) 77.9 min.NonylphenolMW: 220

DMP-30MW: 265

OTBPMW: 150

CNSLMW: 300

2.0% (0.9 g)71.9 min.

2.4% (1.08 g)

75.5 min.

1.36% (0.61 g)

69.3 min.

2.72% (1.22 g)

72.4 min.

4.0% (1.8 g)66.6 min.

4.8% (2.16 g)

75.9 min.

2.72% (1.22 g)

67.1 min.

5.44% (2.44 g)

71.2 min.

8.0% (3.6 g)57.8 min.

9.6% (4.32 g)

73.2 min.

5.44% (2.44 g)

61.5 min.

10.9% (4.88 g)

65.6 min.

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Geltime Study @ 25°C

DETA Phenalkamine: A.N. : 518 mgKOH/g(RoyOxy™ RA-950) AHEW : 81 Vis.@25°C : 1280 cP Geltime : (30g/70g BLR) 37.8 min.

NonylphenolMW: 220

DMP-30MW: 265

OTBPMW: 150

CNSL:MW: 300

2.0% (0.60 g)

37.0 min.

2.4% (0.72 g)

40.7 min.

1.36% (0.41 g)

35.2 min.

2.72% (0.82 g)

36.4 min.

4.0% (1.2 g)33.7 min.

4.8% (1.44 g)

40.5 min.

2.72% (0.82 g)

31.8 min.

5.44% (1.64 g)

34.5 min.

8.0% (2.4 g)30.6 min.

9.6% (2.88 g)

39.6 min.

5.44% (1.64 g)

27.2 min.

10.88% (3.27 g)

29.3 min.

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Geltime Study @ 5°C

DETA Phenalkamine: A.N. : 518 mgKOH/g(RoyOxy™ RA-950) AHEW : 81 Vis.@25°C : 1280 cP Geltime : (30g/70g BLR) 114.7 min.

NonylphenolMW: 220

DMP-30MW: 265

OTBPMW: 150

CNSL:MW: 300

2.0% (0.60 g)

90.7 min.

2.4% (0.72 g)

108.1 min.

1.36% (0.41 g)

84.2 min.

2.72% (0.82 g)

88.1 min.

4.0% (1.2 g)60.5 min.

4.8% (1.44 g)

112.1 min.

2.72% (0.82 g)

55.2 min.

5.44% (1.64 g)

56.5 min.

8.0% (2.4 g)46.4 min.

9.6% (2.88 g)

107.1 min.

5.44% (1.64 g)

36.4 min.

10.88% (3.27 g)

41.6 min.

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Geltime Study @ 25°C

Mixed Phenalkamine: (RoyOxy RA-59 & A.N. : 343mgKOH/g RoyOxy RA-59LC) AHEW : 95 Vis. @25°C : 1317 cP Geltime : (34g/66g BLR) 38.3 minNonylphenolMW: 220

DMP-30MW: 265

OTBPMW: 150

CNSL:MW: 300

2.0% (0.68 g)

37.2 min.

2.4% (0.82 g)

38.0 min.

1.36% (0.46 g)

37.3 min.

2.72% (0.93 g)

37.5 min.

4.0% (1.36 g)

34.0 min.

4.8% (1.63 g)

35.2 min.

2.72% (0.93g)

35.1 min.

5.44% (1.85 g)

35.0 min.

8.0% (2.72 g)

32.5 min.

9.6% (3.26 g)

33.9 min.

5.44% (1.85 g)

32.3 min.

10.88% (3.70g)

31.1 min.

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Geltime Study @ 5°C

Mixed Phenalkamine: (RoyOxy™ RA-59 & A.N. : 343mgKOH/g RoyOxy™ RA-59LC) AHEW : 95 Vis.@25°C : 1317 cP Geltime : (34g/66g BLR) 105.3 min.

NonylphenolMW: 220

DMP-30MW: 265

OTBPMW: 150

CNSL:MW: 300

2.0% (0.68 g)

82.8 min.

2.4% (0.82 g)

88.1 min.

1.36% (0.46 g)

95.1 min.

2.72% (0.93 g)

100.3 min.

4.0% (1.36 g)

76.3 min.

4.8% (1.63 g)

89.0 min.

2.72% (0.93g)

85.5 min.

5.44% (1.85 g)

86.2 min.

8.0% (2.72 g)

69.1 min.

9.6% (3.26 g)

87.5 min.

5.44% (1.85 g)

78.5 min.

10.88% (3.70g)

81.8 min.

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DGEBA / EDA Phenalkamine (RoyOxy™ RA-951) Water Intake DataThickness of Cured Bar: 10mmCured @ 25°C for 24 hrs. , then immersed in 20°C Water for 10 days

Catalyst

Level

None(Nea

t)

Nonyl-Phenol4.0%

1.80 phr

Nonyl-Phenol8.0%

3.60 phr

DMP-30

4.8%2.16 phr

DMP-30

9.6%4.32 phr

% of WaterIntake

0.291%

0.291% 0.295% 0.417%

0.601%

ExtraWaterIntake

N/A None ( 0 )

0.04% 0.126%

0.310%

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Gelation with DGEBA - Geltime @25°C

NonylphenolMW: 220

DMP-30MW: 265

4.0% (w/w)Stable

4.0%(w/w)Geltime: 119 min

10.0% (w/w)Stable

10.0% (w/w)Geltime: 48 min.

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CONCLUSION - I

I) I) In Phenalkamine / Epoxy System: “Phenol Moiety” Alone is better than

DMP-30 (Combination of “Phenol” and “BDMA-Tertiary Amine”)

II) At 25 °C: Similar Acceleration Effect for all phenols disregard whether it is

a) Ortho / Para / Meta- substitutions b) Linear Alkyl/Bulky Alkyl/ Linear

Alkenyl c) Molecular Weight ROYCE INTERNATIONAL

CONCLUSION - II

III) At 5 °C: Nonylphenol performs best may contribute from:

a) Lower Molecular Weight (vs. CNSL) b) Linear alkyl substitution at “Para” position versus Bulky alkyl at “Ortho” position (vs. OTBP) IV) Nonylphenol will not cause extra water intake up to 3.6 phr level, however, DMP-30 causes significant water intake even at 2.16 phr (40% more) and at 4.32 phr (100% more). It might due to the presence of “BDMA Tertiary amine moiety”.

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CONCLUSION - III

V) DMP-30 shows no accelerating effect for DETA Phenalkamine (i.e. RoyOxy RA-950) both at 25 and 5°C. This is also true for mixed Phenalkamine (i.e. RoyOxy RA-59) at 5⁰C.

VI) In the mixed Phenalkamine / Epoxy System:For All Phenols: The Accelerators behave more closer to EDA Phenalkamine / Epoxy System at both 25 and 5⁰C.

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