7. Mannich Reaction and Mannich Base
Mannich Reaction: (amino-alkylation of acidic proton named after
chemist Carl Mannich )
Mannich Bases: ( for Example: I & II )
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8. Phenalkamines
Mannich Base based on Phenols:
Phenol, Cresol, tButylphenol, Nonylphenol etc….
Drawback: Solid at RT (liquid product may contain more than 30% of free
phenol).
Phenalkamines: Based on CNSL
MW = 300
( R = C15H27 )
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9. Advantage of Phenalkamines as
Hardeners for Epoxy
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
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10. Reactivity Study - Gelation
Techne 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-59
3)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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11. Phenalkamines selected in this Study
I)
EDA Phenalkamine:
i.e. RoyOxy™ RA-951
Fast Cure, Low Blushing, Excellent Corrosion
Resistance, High Viscosity
II) DETA Phenalkamine:
i.e. RoyOxy™ RA-950
Fast Cure, Low Viscosity, Some Blushing
III) Mixed (EDA/DETA) Phenalkamine:
i.e. RoyOxy™ RA-59, RoyOxy™ RA-59 LC
Low Viscosity, Low Blushing, Excellent for
Flooring Application
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12. Geltime Study @ 25 C
EDA Phenalkamine
(RoyOxy™ RA-951)
A.N.
:
AHEW
:
Vis. @25 C :
Geltime
:
316 mgKOH/g
130
27,200 cP
(45g/55g BLR) 71 min.
Nonylphenol
MW: 220
DMP-30
MW: 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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13. Geltime Study @ 25 C
EDA Phenalkamine
(RoyOxy™ RA-951)
Nonylphenol
MW: 220
A.N.
AHEW
Vis. @25 C
Geltime
DMP-30
MW: 265
: 316 mgKOH/g
: 130
: 27,200 cP
: (45g/55g BLR) 71 min.
OTBP
MW: 150
CNSL
MW: 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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14. Geltime Study @ 5 C
EDA Phenalkamine
(RoyOxy™ RA-951)
Nonylphenol
MW: 220
A.N.
: 316 mgKOH/g
AHEW
: 130
Vis. @25 C : 27,200 cP
Geltime
: (45g/55g BLR) 77.9 min.
DMP-30
MW: 265
OTBP
MW: 150
CNSL
MW: 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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15. Geltime Study @ 25 C
DETA Phenalkamine:
(RoyOxy™ RA-950)
Nonylphenol
MW: 220
A.N.
AHEW
Vis.@25 C
Geltime
DMP-30
MW: 265
:
:
:
:
518 mgKOH/g
81
1280 cP
(30g/70g BLR) 37.8 min.
OTBP
MW: 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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16. Geltime Study @ 5 C
DETA Phenalkamine:
(RoyOxy™ RA-950)
Nonylphenol
MW: 220
A.N.
AHEW
Vis.@25 C
Geltime
DMP-30
MW: 265
:
:
:
:
518 mgKOH/g
81
1280 cP
(30g/70g BLR) 114.7 min.
OTBP
MW: 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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17. Geltime Study @ 25 C
Mixed Phenalkamine:
(RoyOxy RA-59 &
RoyOxy RA-59LC)
Nonylphenol
MW: 220
A.N.
AHEW
Vis. @25 C
Geltime
DMP-30
MW: 265
:
:
:
:
343mgKOH/g
95
1317 cP
(34g/66g BLR) 38.3 min
OTBP
MW: 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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18. Geltime Study @ 5 C
Mixed Phenalkamine:
(RoyOxy™ RA-59 &
RoyOxy™ RA-59LC)
Nonylphenol
MW: 220
A.N.
AHEW
Vis.@25 C
Geltime
DMP-30
MW: 265
: 343mgKOH/g
: 95
: 1317 cP
: (34g/66g BLR) 105.3 min.
OTBP
MW: 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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19. DGEBA / EDA Phenalkamine (RoyOxy™ RA-951)
Water Intake Data
Thickness of Cured Bar: 10mm
Cured @ 25 C for 24 hrs. , then immersed in 20 C Water for 10 days
Catalyst
Level
None
(Neat)
Nonyl-Phenol
4.0%
1.80 phr
Nonyl-Phenol
8.0%
3.60 phr
% of
Water
Intake
0.291
%
0.291%
0.295%
0.417%
0.601%
N/A
None
(0)
0.04%
0.126%
0.310%
Extra
Water
Intake
DMP-30 DMP-30
4.8%
9.6%
2.16 phr 4.32 phr
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20. Gelation with DGEBA - Geltime @25 C
Nonylphenol
MW: 220
DMP-30
MW: 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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21. 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
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22. 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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23. 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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