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9/25/2007 Page 1
A new Cycloaliphatic Amine for
Coatings and Composites Applications
Rajesh Turakhia, Bill Dellinger, Deb Bhattacharjee, John ArgyropoulosDow Chemical Company, Freeport, Texas 77541
9/25/2007 Page 2
Presentation Contents
• New Cycloaliphatic Amine and Regulatory Status• Commercial Cycloaliphatic Amines• Mechanism and Rate Constants
• Reactivity comparison • Performance Evaluation of the amine and amine adduct
• Material Properties• Composites Application• Coatings Application
• Commercial Status• Conclusions
* Trademark of Dow Chemical Company
9/25/2007 Page 3
New Cycloaliphatic Amine
Structure
1
65
4
23
7NH2 8 9
NH210 1
23
4
65
7NH2 8
9
NH210
CAS 2549-93-1CAS 2579-20-6
Mixture of cis and trans 1,3-bis(aminomethyl)cyclohexane (CAS 2579-20-6) and 1,4-bis(aminomethyl)cyclohexane (CAS 2549-93-1)
Applications
As a amine hardener and as amine-adduct hardener in coatings and composites applications.
9/25/2007 Page 4
Regulatory Listings
CAS 2579-20-6Current Regulatory Listings: ASIA-PACIFIC: ASIA-PAC; AUSTRALIA: AICS; CANADA: DSL, NDSL; EEC: EINECS; JAPAN: ENCS; KOREA: ECL; PHILIPPINES: PICCS; USA: TSCA
CAS 2549-93-1Current Regulatory Listings: CANADA: NDSL, WHMIS; EEC: EINECS; USA: TSCA
For the rest of the presentation the mixture of cis and trans 1,3-bis(aminomethyl)cyclohexane (CAS 2579-20-6) and 1,4-bis(aminomethyl)cyclohexane (CAS 2549-93-1) will be referred as 1,3/1,4-BMAC
9/25/2007 Page 5
Commercial Cycloaliphatic Amines
Major Commercial Cycloaliphatic Amines
Cycloaliphatic Amines Suppliers Molecular Weight Amine Equivalent Weight
1,3-BAC Mitsubishi 142.2 35.6
IPDA Degussa 170.3 42.6
NBDA Mitsui 154.3 38.6
CHDA4/Amicure® PACM BASF/Air Products 210.3 52.6
1,2 DACH Multiple 114 28.5
® Trademark of Air Products
Some of these commercial products may have multiple suppliers
9/25/2007 Page 6
Commercial Cycloaliphatic Amines
Consumption of Cycloaliphatic Amine Hardeners by Type (Unformulated)Total Size 105 MM lb
IPDA51%
DACH7%
PACM14%
Polycycloaliphatic25%
1,3 BAC2%
MACM1%
2005 Data Source: unknown
9/25/2007 Page 7
Mechanism of the curing of epoxy by amines
RHC CH2
O
+ RNH2 RHC
OH
H2C NHR'
RHC CH2
O
+ RHC
OH
H 2C N
R
RHC
OH
H2C NHR' C
H 2CH
HO
R
primary amineepoxy secondary amine
epoxy secondary amine tertiary amine
• The lone pair of the primary amine attacks the CH2-epoxy group via a SN2 mechanism• The amine exclusively attacks the methylene group• The addition reaction forms a hydroxyl group and a secondary amine• The lone pair of the secondary amine attacks the CH2-epoxy group via a SN2 mechanism• The addition reaction forms a hydroxyl group and a tertiary amine
9/25/2007 Page 8
Structure Details and Comparison with IPDA
NH2
NH2
CH3 NH2
CH3 CH3
NH21,3/1,4-BMAC
NH2 NH2
IPDA
Primary amine on a primary carbon atom
Primary amine on a secondary carbon atom (ring carbon)
9/25/2007 Page 9
Rate Constants Comparison (Computational Method)
Primary Amine Secondary Amine Primary Amine Secondary Amine
Temperature k1N k2N k1N k2N
170ºC 2.10X10-15 2.09X10-15 0.69X10-15 -
200ºC 3.57X10-14 3.44X10-14 1.28X10-14 0.077X10-14
240ºC 9.54X10-13 8.68X10-13 3.73X10-13 0.22X10-13
* The rate constant is for the primary amine directly to the cyclohexyl ring and the secondary amine is the one formed from the reaction of primary amine
1,3/1,4-BMAC IPDA*IPDA
NH2
NH2
CH3 NH2
CH3 CH3
NH2
CH3 NH2
CH3 CH3
NH2
NH2 NH2
Spartan® MO program packageCourtesy of M. Marks and N. Rondan, Dow Chemical Company
9/25/2007 Page 10
Rate Constants Comparison (Computational Method)
• The primary amino group directly to the ring in IPDA is 3X times slower than the 1,3/1,4-BMAC primary amino group
• The secondary amino group formed from the reaction of the primary amine connected directly to the ring in IPDA is 50X times slower than the similar secondary amino group in 1,3/1,4-BMAC
Spartan® MO program packageCourtesy of M. Marks and N. Rondan, Dow Chemical Company
9/25/2007 Page 11
Amine Reactivity Comparison
Liquid Epoxy Resin/Cycloaliphatic amines – DSC Analysis
1,3/1,4-BMAC is more reactive than IPDA
Reactivity of cycloaliphatic amine hardeners with LERAmbient Cure Condition
50
55
60
65
70
75
80
85
0 50 100
150
200
250
300
Time (hrs)
Con
vers
ion
(%)
IPDA1,3/1,4-BMACAncamine* PACM
9/25/2007 Page 12
Amine Reactivity Comparison
Liquid Epoxy Resin/Cycloaliphatic amines – DSC AnalysisReactivity of cycloaliphatic amine hardeners with LER
Ambient Cure Condition
50
55
60
65
70
75
80
85
0 10 20 30 40 50 60 70 80 90 100
Time (hrs)
Con
vers
ion
(%)
IPDA1,3/1,4-BMACAncamine* PACM
Reactivity in first 100 hours
9/25/2007 Page 13
Amine Reactivity Comparison
Liquid Epoxy Resin/Cycloaliphatic amines – DSC Analysis
Reactivity of cycloaliphatic amine hardeners with LERAmbient Cure Condition
50
55
60
65
70
75
80
85
0 50 100
150
200
250
300
Time (hrs)
Con
vers
ion
(%) 1,3-BAC
1,3/1,4-BMAC
1,3/1,4-BMAC is slightly faster than 1,3-BAC
9/25/2007 Page 14
Rheokinetic Modeling
Rate Constant K1
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
1.E-04
1.E-03
1.E-02
1.E-01
0 50 100 150 200
Temperature (ºC)
Rat
e C
onst
ant (
1/Se
c)
LER_1,3/1,4-BMAC
LER_IPDA
LER_PACM
9/25/2007 Page 15
Rheokinetic Modeling
Rate Constant K2
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
1.E-04
1.E-03
1.E-02
1.E-01
0 50 100 150 200
Temperature (ºC)
Rat
e C
onst
ant (
1/Se
c)
LER_1,3/1,4-BMAC
LER_IPDA
LER_PACM
383_AEP
9/25/2007 Page 16
Rheokinetic Modeling
Conversion
0.0
0.2
0.4
0.6
0.8
1.0
0 100 200 300 400Time (Min)
Deg
ree
of C
ure
LER_1,3/1,4-BMAC LER_IPDA LER_PACM
\
9/25/2007 Page 17
Epoxy - Amine Formulations
Epoxy-Amine Formulations and Clear Castings
Cycloaliphatic Amines Amine HEW LER EEW Amine Wt. % LER Wt. %
1,3-1,4/BMAC 35.6 188.4 15.9 84.1
IPDA 42.6 188.4 18.4 81.6
• Made 1/8’’ clear castings• Curing Condition: 150ºC / 3h
9/25/2007 Page 18
Epoxy - Amine Formulations
Evaluation of fully cured clear castings
Material Properties Comparison
Cycloaliphatic Amines Tg* Tensile Strength Tensile Modulus % Strain @ Break
(ºC) MPa GPa (%)
1,3/1,4/BMAC 145 84 2.6 7.30 ± 0.61
IPDA 160 90 2.8 7.31 ± 0.18
* DMTA ASTM D638
IPDA has a high final Tg for a fully cured systemComparable Material Properties
9/25/2007 Page 19
Epoxy - Amine Formulations
Improved Fracture Toughness for 1,3/1,4-BMAC
Fracture Toughness Comparison
0.8264
0.5961
0.0000
0.1000
0.2000
0.3000
0.4000
0.5000
0.6000
0.7000
0.8000
0.9000
1.0000
IPDA 1,3/1,4-BMAC
Frac
ture
Tou
ghne
ss, K
1c (M
Pa.m
1/2)
Evaluation of fully cured clear castings
ASTM D5045
9/25/2007 Page 20
Amine Adduct Preparation and Properties
Cycloaliphatic Amines
Weight % Amine
Weight % LER Adduct AEW
Viscosity mPa.s @ 25ºC
1,3-BAC 75.2 24.8 50.2 440
IPDA 78.5 21.6 57.8 2846
NBDA 76.7 23.3 53.2 1406
CHDA 81.8 18.2 68.1 20,259
1,3-1,4/BMAC 75.2 24.8 50.4 554
•Synthesis Ratio: Amine:LER:: 8:1 (molar ratio)•Synthesis condition: 80ºC/2h
9/25/2007 Page 21
Epoxy – Amine Adduct Formulations
Epoxy-Amine Adduct Formulations and Clear Castings
Cycloaliphatic Amine Adducts Adduct HEW LER EEW Amine Wt. % LER Wt. %
1,3-BAC 50.2 188.4 21.1 78.9
IPDA 57.8 188.4 23.5 76.5
NBDA 53.2 188.4 22.0 78.0
CHDA 68.1 188.4 26.6 73.4
1,3-1,4/BMAC 50.4 188.4 21.1 78.9
• Made 1/8’’ clear castings• Curing Condition: 150ºC / 3h
9/25/2007 Page 22
Epoxy – Amine Adduct Formulations
Evaluation of fully cured clear castings
Material Properties Comparison
Cycloaliphatic Amines Tg* Tensile Strength Tensile Modulus % Strain @ Break
(ºC) MPa GPa (%)
1,3-BAC 142 85 2.5 7.48±0.73
IPDA 158 87 2.3 7.51±0.43
NBDA 145 84 2.6 7.64±0.14
CHDA 165 84 2.3 7.00±0.78
1,3-1,4/BMAC 142 83 2.5 7.21±0.64
Some variation in Tg Comparable Material Properties
9/25/2007 Page 23
Epoxy – Amine Adduct Formulations
Improved Fracture Toughness for NBDA and 1,3/1,4-BMAC
Evaluation of fully cured clear castings
Fracture Toughness Comparison
0.7570.793
0.999
0.884
0.663
0.000
0.200
0.400
0.600
0.800
1.000
1.200
IPDA Adduct 1,3/1,4-BMAC Adduct NBDA Adduct 1,3-BAC Adduct CHDA Adduct
Frac
ture
Tou
ghne
ss, K
1c (M
Pa.m
1/2)
9/25/2007 Page 24
Wind Blade ApplicationInfusion System
Rheokinetic Modeling
9/25/2007 Page 25
Reactivity
Rate Constant K1
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
1.E-04
1.E-03
1.E-02
1.E-01
0 50
Temperature (ºC)
Rat
e C
onst
ant (
1/Se
c)
Experimental 1
Experimental 2
Experimental 3
Experimental 4
Control
9/25/2007 Page 26
Degree of Cure
0.6
0.8
1.0
0 200 400 600 800 1000Time (Min)
Deg
ree
of C
ure
0
50
100
150
200
Tem
pera
ture
(ºC
)
Experimental 1 Experimental 2 Experimental 3
Experimental 4 Control Temp
\
9/25/2007 Page 27
Tg Development
0
10
20
30
40
50
60
70
80
90
0 200 400 600 800 1000 1200Time (Min)
Tem
pera
ture
(ºC
)
Experimental 1 Experimental 2 Experimental 3 Experimental 4
Temp Control Step Marks
\
9/25/2007 Page 28
Viscosity Development
1.E-2
1.E+0
1.E+2
1.E+4
1.E+6
1.E+8
0 50 100 150 200 250 300Time (Min)
Vis
cosi
ty (P
a-Se
c)
0
50
100
150
200
Tem
pera
ture
(ºC
)
Experimental 1 Experimental 2 Experimental 3
Experimental 4 Control Temp
\
9/25/2007 Page 29
Amine Adduct Formulations
Comparison of a epoxy thermoset formulation with a commercial curing agent
Formulation Details
Formuations Amine AHEW LER EEW Amine % LER %
Ancamine* 1618 113.00 188.4 37.5 62.5
1,3/1,4-BMAC Adduct w/ 20% Benzyl Alcohol 63.05 188.4 25.1 74.9
1,3/1,4-BMAC Adduct w/ 40% Benzyl Alcohol 84.07 188.4 30.9 69.1
1,3/1,4-BMAC Adduct w/ 60% Benzyl Alcohol 126.10 188.4 40.1 59.9
* Trademark of Air Products
9/25/2007 Page 30
Physical Properties Development
Epoxy-Amine Adduct Systems
Formuations 1 day 3 days 7 days 1 day 3 days 7 days
Ancamine* 1618 HB F F 78 127 137
1,3/1,4-BMAC Adduct w/ 20% Benzyl Alcohol H H H 148 153 150
1,3/1,4-BMAC Adduct w/ 40% Benzyl Alcohol F F F 132 137 131
1,3/1,4-BMAC Adduct w/ 60% Benzyl Alcohol 2B 2B B 57 81 102
Softest 4B-3B-2B-B-HB-F-H-2H-3H-4H-5H-6H Hardest
Pencil Hardness Konig Pendulum Hardness (osc)
Dust Free Dry ThroughFormuations (hr) (hr)
Ancamine* 1618 7 151,3/1,4-BMAC Adduct w/ 20% Benzyl Alcohol 3.5 5.51,3/1,4-BMAC Adduct w/ 40% Benzyl Alcohol 4 61,3/1,4-BMAC Adduct w/ 60% Benzyl Alcohol 6 9
19.5º C and 25% humidity
Thin Film Dry Times
Faster dust free and dry through times and faster hardness development over 7 days for 1,3/1,4-BMAC systems
9/25/2007 Page 31
Coating Properties
Epoxy-Amine Adduct Systems7 day ambient cure
Formuations 20º 60º 85º Forward Reverse Apprearance Tg ºC)Cross Hatch
Adhesion
Ancamine* 1618 113 124 101 20 <10 Good 73.6 4B1,3/1,4-BMAC Adduct w/ 20% Benzyl Alcohol 113 126 100 20 <10 Good 107.5 4B1,3/1,4-BMAC Adduct w/ 40% Benzyl Alcohol 114 124 98 40 20 Good 78.1 4B
1,3/1,4-BMAC Adduct w/ 60% Benzyl Alcohol 118 127 98 160 160 Good 64.9 5B
5B = No loss
0B = >65% loss
Impact (in-lb)Gloss
• Improved or comparable properties for 1,3/1,4-BMAC systems
9/25/2007 Page 32
External Evaluation
• Better adhesion (lap shear)• Better hydrolytic stability• Less Yellowing• Better reactivity
• Blush• Solt Fog• UV
9/25/2007 Page 33
Commercial Availability
1,3/1,4-BMAC
• We have produced in drum quantities for internal testing
• We are working internally and with external toll manufacturers to produce the amine on a commercial level
• Like other cycloaliphatic amines, 1,3/1,4-BMAC requires specialized high pressure amination equipment in the manufacturing process
9/25/2007 Page 34
9/25/2007 Page 35
Conclusions
• We have a new cycloaliphatic amine hardener• It has a high reactivity with liquid epoxy resin• 1,3/1,4-BMAC is on TSCA and EINECS• We have successfully evaluated in coatings and composites (wind
blade) applications• Commercial availability of 1,3/1,4-BMAC is planned for 2008