A new Cycloaliphatic Amine Coatings and Composites ... · PDF file9/25/2007 Page 1 A new Cycloaliphatic Amine for Coatings and Composites Applications Rajesh Turakhia, Bill Dellinger,

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


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


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


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


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


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


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)


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



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


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


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


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



* 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

Documents

A new Cycloaliphatic Amine Coatings and Composites ... · PDF file9/25/2007 Page 1 A new Cycloaliphatic Amine for Coatings and Composites Applications Rajesh Turakhia, Bill Dellinger,