A new Cycloaliphatic Amine for Coatings and Composites Applications

Rajesh Turakhia, Bill Dellinger, Deb Bhattacharjee, John Argyropoulos Dow Chemical Company, Freeport, Texas 77541

9/25/2007

Page 1

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 2

New Cycloaliphatic Amine

Structure
5 6 4 3 2 9

3 2 4 5 6

NH2
10

H2N
8

1 7

NH2
10

H2N
8

1 7

CAS 2579-20-6

CAS 2549-93-1

Mixture of cis and trans 1,3-bis(aminomethyl)cyclohexane (CAS 2579-20-6) and 1,4bis(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 3

Regulatory Listings

CAS 2579-20-6 Current Regulatory Listings: ASIA-PACIFIC: ASIA-PAC; AUSTRALIA: AICS; CANADA: DSL, NDSL; EEC: EINECS; JAPAN: ENCS; KOREA: ECL; PHILIPPINES: PICCS; USA: TSCA

CAS 2549-93-1 Current 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 4

Commercial Cycloaliphatic Amines

Major Commercial Cycloaliphatic Amines

Cycloaliphatic Amines

Suppliers

Molecular Weight

Amine Equivalent Weight

1,3-BAC IPDA NBDA CHDA4/Amicure PACM 1,2 DACH

Mitsubishi Degussa Mitsui BASF/Air Products Multiple

142.2 170.3 154.3 210.3 114

35.6 42.6 38.6 52.6 28.5

Trademark of Air Products

Some of these commercial products may have multiple suppliers

9/25/2007

Page 5

Commercial Cycloaliphatic Amines

Consumption of Cycloaliphatic Amine Hardeners by Type (Unformulated) Total Size 105 MM lb

MACM 1% Polycycloaliphatic 25%

1,3 BAC 2% PACM 14% DACH 7%

IPDA 51%

2005 Data
9/25/2007

Source: unknown
Page 6

Mechanism of the curing of epoxy by amines

R H C O CH2 H C OH H2 C

RNH2

NHR '

epoxy

primary amine

secondary amine

H C O

CH2

H C OH

H2 C

NHR '

H C OH

H2 C

N R

H2 C

H C OH

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 7

Structure Details and Comparison with IPDA

NH2 H2N

1,3/1,4-BMAC
H3C H3C

NH2

H2N

NH2

CH3 NH2

IPDA
Primary amine on a primary carbon atom Primary amine on a secondary carbon atom (ring carbon)
9/25/2007 Page 8

Rate Constants Comparison (Computational Method)

IPDA 1,3/1,4-BMAC
Primary Amine Temperature 170C 200C 240C k1N 2.10X10 3.57X10 9.54X10
-15 -14 -13

IPDA* Primary Amine k1N

-15 -14 -13

Secondary Amine k2N 2.09X10 3.44X10 8.68X10

Secondary Amine k2N

0.69X10 1.28X10 3.73X10

-15 -14 -13

0.077X10 0.22X10
-14

-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

NH2 H2N
NH2

NH2

H3C H3C

CH3 NH2

H3C H3C

CH3 NH2

H2N

NH2
Spartan MO program package

Courtesy of M. Marks and N. Rondan, Dow Chemical Company

9/25/2007

Page 9

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

Courtesy of M. Marks and N. Rondan, Dow Chemical Company

9/25/2007

Spartan MO program package

Page 10

Amine Reactivity Comparison

Liquid Epoxy Resin/Cycloaliphatic amines DSC Analysis
Reactivity of cycloaliphatic amine hardeners with LER Ambient Cure Condition 85 80 75 70 65 60 55 50 0 50 100 150 200 250 300
IPDA 1,3/1,4-BMAC Ancamine* PACM

Conversion (%)

Time (hrs)

1,3/1,4-BMAC is more reactive than IPDA

9/25/2007 Page 11

Amine Reactivity Comparison

Liquid Epoxy Resin/Cycloaliphatic amines DSC Analysis
Reactivity of cycloaliphatic amine hardeners with LER Ambient Cure Condition 85 80 75 70 65 60 55 50 0 10 20 30 40
Time (hrs)
IPDA 1,3/1,4-BMAC Ancamine* PACM

Conversion (%)

50

60

70

80

90

100

Reactivity in first 100 hours

9/25/2007 Page 12

Amine Reactivity Comparison

Liquid Epoxy Resin/Cycloaliphatic amines DSC Analysis
Reactivity of cycloaliphatic amine hardeners with LER Ambient Cure Condition 85 80 75 70 65 60 55 50 0 50 100
Time (hrs)

Conversion (%)

1,3-BAC 1,3/1,4BMAC

1,3/1,4-BMAC is slightly faster than 1,3-BAC

9/25/2007 Page 13

150

200

250

300

Rheokinetic Modeling Rate Constant K1

1.E-01 1.E-02 1.E-03 Rate Constant (1/Sec) 1.E-04 1.E-05 1.E-06 1.E-07 1.E-08 1.E-09 0 50 100 Temperature (C) 150 200
LER_1,3/1,4-BMAC

LER_IPDA

LER_PACM

9/25/2007

Page 14

Rheokinetic Modeling Rate Constant K2

1.E-01 1.E-02 1.E-03 Rate Constant (1/Sec) 1.E-04 1.E-05 1.E-06 1.E-07 1.E-08
383_AEP LER_1,3/1,4-BMAC LER_IPDA LER_PACM

1.E-09 0 50 100 Temperature (C) 150 200

9/25/2007

Page 15

Rheokinetic Modeling Conversion

1.0 0.8 Degree of Cure

0.6

0.4
\

0.2

0.0 0 100 200 Time (Min) 300 400

LER_1,3/1,4-BMAC

LER_IPDA

LER_PACM

9/25/2007

Page 16

Epoxy - Amine Formulations

Epoxy-Amine Formulations and Clear Castings
Cycloaliphatic Amines 1,3-1,4/BMAC IPDA

Amine HEW 35.6 42.6

LER EEW 188.4 188.4

Amine Wt. % 15.9 18.4

LER Wt. % 84.1 81.6

Made 1/8 clear castings Curing Condition: 150C / 3h

9/25/2007

Page 17

Epoxy - Amine Formulations

Evaluation of fully cured clear castings

Material Properties Comparison

Cycloaliphatic Amines

Tg* (C)

Tensile Strength MPa 84 90

Tensile Modulus GPa 2.6 2.8

% Strain @ Break (%) 7.30 0.61 7.31 0.18

1,3/1,4/BMAC IPDA
* DMTA

145 160

ASTM D638

IPDA has a high final Tg for a fully cured system Comparable Material Properties

9/25/2007

Page 18

Epoxy - Amine Formulations

Evaluation of fully cured clear castings

Fracture Toughness Comparison

1.0000 0.9000

0.8000 Fracture Toughness, K1c (MPa.m1/2)

0.7000

0.8264

0.6000

0.5000

0.5961

0.4000

0.3000

0.2000

0.1000

0.0000

IPDA

1,3/1,4-BMAC

Improved Fracture Toughness for 1,3/1,4-BMAC

9/25/2007

ASTM D5045
Page 19

Amine Adduct Preparation and Properties

Cycloaliphatic Amines 1,3-BAC IPDA NBDA CHDA 1,3-1,4/BMAC

Weight % Amine 75.2 78.5 76.7 81.8 75.2

Weight % LER 24.8 21.6 23.3 18.2 24.8

Adduct AEW 50.2 57.8 53.2 68.1 50.4

Viscosity mPa.s @ 25C 440 2846 1406 20,259 554

Synthesis Ratio: Amine:LER:: 8:1 (molar ratio) Synthesis condition: 80C/2h

9/25/2007

Page 20

Epoxy Amine Adduct Formulations

Epoxy-Amine Adduct Formulations and Clear Castings

Cycloaliphatic Amine Adducts 1,3-BAC IPDA NBDA CHDA 1,3-1,4/BMAC

Adduct HEW 50.2 57.8 53.2 68.1 50.4

LER EEW 188.4 188.4 188.4 188.4 188.4

Amine Wt. % 21.1 23.5 22.0 26.6 21.1

LER Wt. % 78.9 76.5 78.0 73.4 78.9

Made 1/8 clear castings Curing Condition: 150C / 3h

9/25/2007 Page 21

Epoxy Amine Adduct Formulations

Evaluation of fully cured clear castings

Material Properties Comparison

Cycloaliphatic Amines Tg* (C) 1,3-BAC IPDA NBDA CHDA 1,3-1,4/BMAC 142 158 145 165 142 Tensile Strength Tensile Modulus % Strain @ Break MPa 85 87 84 84 83 GPa 2.5 2.3 2.6 2.3 2.5 (%) 7.480.73 7.510.43 7.640.14 7.000.78 7.210.64

Some variation in Tg Comparable Material Properties

9/25/2007 Page 22

Epoxy Amine Adduct Formulations

Evaluation of fully cured clear castings

Fracture Toughness Comparison

1.200

1.000

Fracture Toughness, K1c (MPa.m1/2)

0.800

0.999 0.884

0.793

0.757

0.600

0.663
0.400

0.200

0.000

IPDA Adduct

1,3/1,4-BMAC Adduct

NBDA Adduct

1,3-BAC Adduct

CHDA Adduct

Improved Fracture Toughness for NBDA and 1,3/1,4-BMAC

9/25/2007 Page 23

Wind Blade Application Infusion System

Rheokinetic Modeling

9/25/2007

Page 24

Reactivity

Rate Constant K1
1.E-01 1.E-02 1.E-03 Rate Constant (1/Sec) 1.E-04 1.E-05 1.E-06 1.E-07 1.E-08 1.E-09 0 Temperature (C) 50

Experimental 1 Experimental 2 Experimental 3 Experimental 4 Control

9/25/2007

Page 25

Degree of Cure
1.0 200

150 Degree of Cure

Temperature (C)

0.8

100

50

0.6 0 200 400 600 800 Time (Min)

Experimental 1 Experimental 4 Experimental 2 Control

0 1000

Experimental 3 Temp

9/25/2007

Page 26

Tg Development
90 80 70 Temperature (C) 60 50 40 30 20 10 0 0 200 400 600 Time (Min)
Experimental 1 Temp Experimental 2 Control Experimental 3 Step Marks Experimental 4
\

800

1000

1200

9/25/2007

Page 27

Viscosity Development
1.E+8 200

1.E+6 Viscosity (Pa-Sec) 150 1.E+4 100 1.E+2

\

50 1.E+0

1.E-2 0 50 100 150 200 Time (Min) 250

0 300

Experimental 1 Experimental 4

Experimental 2 Control

Experimental 3 Temp

9/25/2007

Temperature (C)

Page 28

Amine Adduct Formulations

Comparison of a epoxy thermoset formulation with a commercial curing agent

Formulation Details
Formuations Ancamine* 1618 1,3/1,4-BMAC Adduct w/ 20% Benzyl Alcohol 1,3/1,4-BMAC Adduct w/ 40% Benzyl Alcohol 1,3/1,4-BMAC Adduct w/ 60% Benzyl Alcohol Amine AHEW 113.00 63.05 84.07 126.10 LER EEW 188.4 188.4 188.4 188.4 Amine % 37.5 25.1 30.9 40.1 LER % 62.5 74.9 69.1 59.9

* Trademark of Air Products

9/25/2007 Page 29

Physical Properties Development

Epoxy-Amine Adduct Systems
Formuations Ancamine* 1618 1,3/1,4-BMAC Adduct w/ 20% Benzyl Alcohol 1,3/1,4-BMAC Adduct w/ 40% Benzyl Alcohol 1,3/1,4-BMAC Adduct w/ 60% Benzyl Alcohol Pencil Hardness 1 day HB H F 2B 3 days F H F 2B 7 days F H F B Konig Pendulum Hardness (osc) 1 day 78 148 132 57 3 days 127 153 137 81 7 days 137 150 131 102

Softest 4B-3B-2B-B-HB-F-H-2H-3H-4H-5H-6H Hardest

Formuations Ancamine* 1618 1,3/1,4-BMAC Adduct w/ 20% Benzyl Alcohol 1,3/1,4-BMAC Adduct w/ 40% Benzyl Alcohol 1,3/1,4-BMAC Adduct w/ 60% Benzyl Alcohol

Thin Film Dry Times Dust Free Dry Through (hr) (hr) 7 15 3.5 5.5 4 6 6 9 19.5 C and 25% humidity

Faster dust free and dry through times and faster hardness development over 7 days for 1,3/1,4BMAC systems
9/25/2007 Page 30

Coating Properties
Epoxy-Amine Adduct Systems 7 day ambient cure

Gloss Formuations Ancamine* 1618 1,3/1,4-BMAC Adduct w/ 20% Benzyl Alcohol 1,3/1,4-BMAC Adduct w/ 40% Benzyl Alcohol 1,3/1,4-BMAC Adduct w/ 60% Benzyl Alcohol 20 113 113 114 118 60 124 126 124 127 85 101 100 98 98

Impact (in-lb) Forward 20 20 40 160 Reverse <10 <10 20 160 Apprearance Good Good Good Good Tg C) 73.6 107.5 78.1 64.9 Cross Hatch Adhesion 4B 4B 4B 5B

5B = No loss 0B = >65% loss

Improved or comparable properties for 1,3/1,4-BMAC systems

9/25/2007

Page 31

External Evaluation

Better adhesion (lap shear) Better hydrolytic stability Less Yellowing Better reactivity

Blush Solt Fog UV

9/25/2007

Page 32

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 33

9/25/2007

Page 34

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

9/25/2007

Page 35