New Developments in Polyetheramine Curing Agents

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New Developments in Polyetheramine Curing Agents

• David Alexander, Bruce Burton, Howard Klein
• Huntsman Performance Products
• The Woodlands, TX 77381
• Thermoset Resin Formulators Association
• Fall 2005 Meeting
• Ft. Lauderdale, FL
• November 14, 2005

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Outline

1. Introduction polyetheramine products, changes
2. Products for faster curing
3. Products for slower curing
4. Products with new backbones
5. Summary

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JEFFAMINE Polyetheramines

• Monoamines, diamines, and triamines
• Flexible polyether backbone
• Polypropylene glycol, polyethylene glycol-based
• Wide molecular weight range 150 to 5000

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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

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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

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Polyetheramine Structural Elements

• 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

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• 2. Faster curing agents

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Modification of Amine Environment

• For faster cure -
• Aminoethyl, 3-aminopropyl end groups for more
  reactive amines
• No adjacent methyl group
• Amine more exposed

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Modification for Faster Cure
Faster polyetheramines
TEGDA
BAPEG
BAPDEG
PTMEGA-1700
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Modification for Faster Cure
Faster polyetheramines

• Formulated viscosities similar
• Reactivities much higher than conventional
  polyetheramines
• Modifcation necessary for coatings applications

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Modification for Faster Cure
Faster polyetheramines

• 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

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Modification for Faster Cure
Coatings formulations
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Modification for Faster Cure
Coatings properties

• High-build, decorative-type coatings
• Shorter dry times with reactive amines MNP
  inhibits blushing
• Adduction, Mannich base formation possible
  modifications

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• 3. Slower curing agents

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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

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Modification for Slower Cure
Slower polyetheramines

• AHEWs similar, giving similar mix ratios
• Viscosities similar, so formulations similar in
  behavior
• Process essentially same as for existing amines,
  giving low color products

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Modification for Slower Cure
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Modification for Slower Cure
Slower polyetheramines

• Glass transition temperatures slightly higher
  than those of existing products
• Cured resin properties similar good mechanical
  properties

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• 4. New backbone

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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

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Modification of Backbone Structure
New PTMEG-based amines

• PTMEGA-1000
• PPG/PTMEG mix
• 2.0 functionality

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Modification of Backbone Structure
PTMEGA-1000
Curing agent components concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin 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
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Modification of Backbone Structure
PTMEGA-1000
Curing agent components concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin 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
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Modification of Backbone Structure
New PTMEG-based amines

• PTMEGA-1700
• All PTMEG means more exposed amine group
• Mixture of amines contains 2 amine also
  

n 13 x 0, the "monomer, 19 x 1,
the "dimer 78 x2 a few
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Modification of Backbone Structure
PTMEGA-1700
Curing agent components concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, 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
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Modification of Backbone Structure
PTMEGA-1700
Curing agent components concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin concentrations, phr, in standard liquid resin 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
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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