New Developments in Polyetheramine Curing Agents David Alexander, Bruce Burton, Howard Klein...

New Developments in Polyetheramine Curing Agents

David Alexander, Bruce Burton, Howard KleinHuntsman Performance ProductsThe Woodlands, TX 77381

Thermoset Resin Formulators AssociationFall 2005 MeetingFt. Lauderdale, FL

November 14, 2005

Huntsman Performance Products

Outline

1. Introduction – polyetheramine products, changes

2. Products for faster curing

3. Products for slower curing

4. Products with new backbones

5. Summary


H2N

CH3

OO

NH2

CH3

CH3

nO

H3C ONH2

CH3

x y

x

y

z

O

O

OH2N NH2

NH2

Monoamines, diamines, and triamines

Flexible polyether backbone

Polypropylene glycol, polyethylene glycol-based

Wide molecular weight range – 150 to 5000

JEFFAMINE® Polyetheramines


Polyetheramines as Epoxy Curing Agents

Have been commercial for more than 30 years

Variety of advantages in epoxy curing Low viscosity, low color, low vapor pressure Moderate reaction rate Flexible backbone – good cured resin properties –

relatively high elongation

Variety of applications as curing agents Coatings, adhesives, composites Flexibility, impact resistance key properties


Polyetheramine Structural Elements

Amine end groups

In PPG-based amines, primary amine next to methyl group Hindrance means slower

reaction Slower is better in some

applications

Most PEG-based diamines capped with PO, giving same type of amine group as PPG-based amines

O

NH2


Polyether backbones

Polypropylene glycol – most common; relatively hydrophobic; good mechanical properties

Polyethylene glycol – not so common in curing agents; hydrophilic; important in some other applications

Polyetheramine Structural Elements

OO

O

O


2. Faster curing agents


Modification of Amine Environment

For faster cure -

Aminoethyl, 3-aminopropyl end groups for more reactive amines

No adjacent methyl group

Amine more exposed

H2N

O

H2N

O


Modification for Faster Cure

OO

NH2

H2N

OO OH2N NH2

OO NH2

H2N

)[x 8(

8( ) ]

OH2N N

H

ONH2

TEGDA

BAPEG

BAPDEG

PTMEGA-1700

Faster polyetheramines




Formulated viscosities similar

Reactivities much higher than conventional polyetheramines

Modifcation necessary for coatings applications

Gel Time

50

55

60

65

70

75

80

TEGDA BAPEG BAPDEG

amineg

el t

ime,

min

Viscosity

50

150

250

350

450

550

650

750

TEGDA BAPEG BAPDEG PPGDA-230

amine

visc

osi

ty, c

ps




Expected trend in glass transition temperatures; similar to PPGDA-230

Flexural properties similar for group

Thermal shock resistance generally superior for systems cured with low MW linear etherdiamines

Glass Transition Temperature

50556065707580859095

100


amine

Tg

, °C

Flexural Strength

0

5

10

15

20

25


aminefl

exu

ral s

tren

gth

, ksi



Coatings formulations

Formulation : A B C

Liquid Epoxy Resin 100 100 100

TEGDA 15.7

BAPEG 19.3

PPGA-230 26.2

Decoupage Monononylphenol 53.8 55.4 58.5

Aminoethylpiperazine (AEP) 4 4 4

Mix viscosity, cps 1040 942 1400

Gel time, minutes (200 g) 4.5 4.5 13.4

Peak exotherm temperature, ºC 183 178 159


Curing Agent TEGDA BAPEG PPGA-230

Film Thickness in microns, μ 77 78 75 Dry Time, hours a) Set to touch 2.3 1.8 3.8 b) Surface Dry 3.3 2.3 5.3 c) Through Dry 4.1 3.4 6.8Pendulum Hardness, Koenig,

Oscillations, 20ºC, cured 1 day 39 34 22 Oscillations, 20ºC, cured 7 days 68 51 63 Crosscut Adhesion, 7 days, ASTM D 3359-95 Method B: Rating / % Removed with tape

0 / 90 0 / 100 5 / 0

Gloss, 20º, 1 day / 7 days 108 / 109 106 / 108 109 / 111 Gloss, 60º, 1 day / 7 days 123 / 123 116 / 121 123 / 124 Gardner Impact, direct,

in Joules, 7 day cure

Gardner Impact, reverse,

in Joules, 7 day cure

Conical Mandrel Bend Pass Pass PassHigh

gloss,High

gloss,High

gloss,no blush no blush no blush

> 217 149 > 217

Appearance

190 163 > 217

Coatings properties

High-build, decorative-type coatings

Shorter dry times with reactive amines; MNP inhibits blushing

Adduction, Mannich base formation possible modifications


3. Slower curing agents


Modification of Amine Environment

For slower cure – Some applications benefit from

longer working times – e.g. large composite parts

2-aminobutyl groups for less reactive amines

Adjacent ethyl instead of methyl group; amine less exposed

New products – BOTDA – diamine

BOTTA – triamine

Modification for Slower Cure

Slowerpolyetheramines

AHEWs similar, giving similar mix ratios

Viscosities similar, so formulations similar in behavior

Process essentially same as for existing amines, giving low color products

Mix Ratio

05

1015202530354045

BOTDA PPGDA-230

BOTTA PPGTA-400

amine

mix

rat

io, p

hr

Viscosity

0200400600800

10001200140016001800

BOTDA PPGDA-230

BOTTA PPGTA-400

amine

visc

osi

ty, c

ps



Viscosity vs. Time - Cure at 40°C

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00

Time - hours

Vis

co

sit

y -

ce

nti

po

ise

PPGA-230

BOTDA

BOTTA


Slower polyetheramines

Glass transition temperatures slightly higher than those of existing products

Cured resin properties similar; good mechanical properties

Glass Transition Temperature

50

60

70

80

90

100

110

BOTDA PPGDA-230

BOTTA PPGTA-400

amine

Tg, °

C

Flexural Strength

5

7

9

11

13

15

17

19

BOTDA PPGDA-230

BOTTA PPGTA-400

amine

flex

ura

l str

eng

th, k

si


4. New backbone


Modification of Backbone Structure

PTMEG – new backbone for polyetheramines

Higher carbon/oxygen ratio means better water resistance

Better mechanical properties

Used in high-performance TPU formulations



H2NO

OO

NH2( )( ))(

2 x 3

PTMEGA-1000

PPG/PTMEG mix

2.0 functionality

New PTMEG-based amines



PTMEGA-1000

Curing agent components

concentrations, phr, in standard liquid resin

PTMEGA-1000 22 40 33

PPGDA-2000 25

PPGDA-400 44 50 40

PPGTA-400 33

Properties

Viscosity, cps 700 600 450 1800

Tg, °C 35 33 25 43



Curing agent components concentrations, phr, in standard liquid resin

PTMEGA-1000 22 22 40 40 33 33

PPGDA-2000 25 25

PPGDA-400 44 44 50 50 40 40

PPGTA-400 33 33

Accelerator 399 10 10 10 5

heat rt heat rt heat rt heat rt

Flexural strength, psi 5500 -- -- -- -- -- 11500 7600

Flexural modulus, psi 195000 -- -- -- -- -- 337000 230000

Tensile strength, psi 3500 2400 1700 1700 1250 570 6500 4100

Elongation at break, % 115 125 86 73 145 95 12 48

% Wt gain, 24 hr water boil 2.7 2.8 2.6 1.2 2.4 2.6 2.5 4.3

% Wt gain, 3 hr acetone boil 23 25 30 33 33 27 15 20

PTMEGA-1000



OH2N N

H

ONH2)[

x n(

n( ) ]

PTMEGA-1700

All PTMEG means more exposed amine group

Mixture of amines; contains 2° amine also

New PTMEG-based amines

n = 13 x = 0, the "monomer,” [~19%] x = 1, the "dimer” [~78%]; x=2 a few %



PTMEGA-1700

Curing agent componentsconcentrations, phr, in standard liquid resin

PTMEGA-1700 26 35 35

PPGDA-2000 25

PPGDA-400 52 50

DGA 24

MEA 14

Properties

Viscosity, cps 800 600 950 1800

Gel time, min 46 35

Tg, °C 28 33 22 40



PTMEGA-1700

Curing agent components concentrations, phr, in standard liquid resin

PTMEGA-1700 26 26 35 35 35 35

PPGDA-2000 25 25

PPGDA-400 52 52 50 50

DGA 24 24

MEA 14 14

Accelerator 399 5 10

Cure conditions heat rt heat rt heat rt heat rt

Flexural strength, psi -- -- -- -- -- -- 6600 --

Flexural modulus, psi -- -- -- -- -- -- 180000 --

Tensile strength, psi 2150 2000 1700 1700 -- 2150 5150 4300

Elongation at break, % 100 150 86 73 -- 300 150 136

% Wt gain, 24 hr water boil 2.2 3.9 2.6 1.2 6.4 6.4 5.5 5.7

% Wt gain, 3 hr acetone boil 29 28 30 33 42 42 27 31


Summary

Variations in polyetheramine structure lead to variations in epoxy curing properties

Amine end group environment Backbone structure

Expanding range of polyetheramine structures, applications

Slower amines for longer working time, good properties Faster amines for more versatility in formulating New polymer backbones for improved properties

New Developments in Polyetheramine Curing Agents David Alexander, Bruce Burton, Howard Klein...

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