Thermo-latent

curing agents for

low temperature 1K
epoxy adhesive
applications

Virtual Innovation Day | May 5th 2021

Dr. Sebastian Clermont

1
Before we get started – the categories to remember for todays topic

°C °C
✓
Long latency Low activation High Temperature High adhesive
temperature reactivity/High stability strength
Green-
Strength
capabilities

2 Virtual Innovation Day | May 5th 2021 | SpecialChem

We will talk about high strength structural epoxy adhesives

°C
✓ =
Type 1K Epoxy 2K Epoxy 2K MMA 2 step Acrylic 2K PU 1K PU SMP Silicone

• Highest • High strength • Plastic • Very fast • Fatigue • Elasticity • Elasticity • High temp
Performance

Strength & toughness Bonding fixture Resistance • Fast fixture • Gap-filling resistance
• Chemical & • Chemical& • Impact • Easy to use • Multi- • Multi- • Multi- • Elasticity
temperature temperature Resistance • Versatile substrate substrate Substrate • Gap-filling
resistancy resistancy • Fast Cure • Toughness • Low cost • Low cost • Non-hazard

Rigid bonding Elastic bonding

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 But first of all..
..who are we?

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Crosslinkers are part of the Evonik’s Specialty Additive Division

Nutrition & Care Specialty Additives Smart Materials Performance Materials

Products for use in the Environmentally friendly Innovative materials that Polymer materials and
areas consumer goods, and energy-efficient enable resource-saving intermediates mainly for
nutrition and health systems as solutions for solutions and replace the rubber, plastics and
several industries conventional materials. agriculture industries

Business Lines : Business Lines: Business Lines: Business Lines:

• Animal Nutrition • Coating Additives • Active Oxygens • Coating Additives
• Care Solutions • Comfort & Insulation • Catalysts • Comfort & Insulation
• Health Care • Interface & Performance • Coating & Adhesive • Interface & Performance
Resins •
• Crosslinkers Crosslinkers
• High Performance •
• Oil Additives Polymers
Oil Additives

• Silanes
• Silica

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Ambition and Positioning Crosslinkers Epoxy Curing Agents
#1 Epoxy Hardener Supplier in the World

▪ Global Revenue about € 450 M

▪ Serving the Coatings, Civil Engineering, Composites & Adhesives market
▪ Global footprint (EMEA, Americas, APAC)

Crosslinkers‘s position:
▪ Offering neat amines, curing
agents / building blocks for epoxy
curing
▪ Support and exchange with
customers for new developments
Customers position:
▪ Adhesives manufacturer
▪ Drive materials innovation
▪ Set and change industry standards
Synergies & Opportunities:
▪ Effective and fast product development
▪ Customers can utilize crosslinkers toolbox for
high performance adhesives and sealants
▪ Evonik offering dedicated support for high
performance applications

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Epoxy Adhesives Curing Agents Markets we support
– a broad range of high-performance applications

Automotive Product Assembly Electronic & Electrical Aerospace

1K/2K Adh. + Sealants 2K Adhesives 1K/2K Adhesives 1K/2K Adhesives

Application

▪ OEM- and aftermarket ▪ Wind Energy ▪ Printed Circuit Boards ▪ Aircraft Interiors
applications ▪ Industrial Assembly ▪ Battery Sealants ▪ Aerospace Structure
▪ PVC Plastisol Sealant ▪ DIY Applications ▪ Potting & Encapsulation

▪ ▪ (Cyclo) aliphatic Amines ▪ (Cyclo) aliphatic Amines ▪

Chemistry

Dicyandiamide Dicyandiamide
▪ Mod. amines + Imidazoles ▪ Polyamides ▪ Phenolic Tertiary Amines ▪ Mod. amines + Imidazoles
Key

▪ (Cyclo) aliphatic Amines ▪ Reactive Diluents ▪ Mod. Amines + Imidazoles ▪ Aliphatic Amines
▪ Polyamides ▪ Reactive Diluents

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 Your partner
ECA – Products Range for tailor-made
solutions

Aliphatic & cycloaliphatic amine curing agents Polyamide and amidoamine curing agents for Waterborne epoxy curing agents for industrial
for use across all major epoxy applications use across all major epoxy applications flooring and protective coatings

Polycarbamide curatives for HDI trimer for Dicyandiamide (DICY) for one component heat
Mono- and difunctional reactive diluents
industrial coatings and floorings cure adhesives and composites

Specialty waterborne epoxy resins for flooring PUD acrylic hybrid dispersion for industrial
coatings Imidazole accelerators
and industrial coating applications

VESTALITE®
Blocked isocyanates and polyamide adhesion Waterborne epoxy curing agents for industrial Epoxy curing agents and PUR based resin
promoters for PVC plastisols flooring and protective coatings formulations for automotive lightweight solutions

1K Adhesives relevant* 2K Adhesives relevant* Adhesion promoter*

8 Virtual Innovation Day | May 5th 2021 | SpecialChem *for indication only, not exhaustive
 What is our motivation?

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Current demands and trends for structural adhesives

High material performance Green and safe material Cost effective

solutions

Durability Sustainability Efficiency

▪ Superior bonding performance
▪ Improved impact and chemical resistance
Usability
▪ Substitution of conventional bonding
and fastening techniques
▪ Bonding of dissimilar materials, e.g. in
automotive 1K applications (lightweight)
▪ Comply with more stringent regulations
▪ Reduced VOC
▪ Bio-based raw materials
▪ Reduced process energy consumption
▪ De-bonding on demand (→ recycling)
▪ Increased productivity, faster cycle times
▪ Lower curing temperatures
▪ Functional adhesives → fewer raw
materials required, e.g. nanoengineered
adhesives, fire retardants

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State of the art of thermo-latent curing agents for low temperature 1K epoxy
adhesive applications

Type
DICY/Accelerators Imidazoles Solid Adducts

Onset
Down to ~120°C Down to ~80°C Down to ~100°C
Temperature

Shelf-life @ 40°C > 1 month > 1 month > 3 months

✓ Adjustable onset temperature ✓ Large spectrum of reactivities ✓ Low onset temperature

Advantages ✓ Good balance of physical properties ✓ Low onset temperature ✓ Good balance of physical properties
✓ Good heat and chemical resistance ✓ Excellent adhesive characteristics ✓ Good heat and chemical resistance
✓ Labelling ✓ High heat and chemical resistance
✓ Labeling

- Moderate to short shelf-life (trade off - Moderate to short shelf-life (trade off - Higher use levels (sole curing
Drawbacks reactivity vs shelf-life) reactivity vs shelf-life) agents)
- In some cases labeling - Pricing
- Pricing

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Setting the target for our development

°C °C
✓
Longer Lower High Temperature High adhesive
latency activation reactivity/Impr stability strength
temperature oved Green-
Strength
development

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Evonik’s toolbox of curing agents for 1K epoxy adhesives

Curing Technology Handling Properties Cured Properties

• Very long latency

Dicyandiamide (DICY) • Good balance of physical properties
• High activation temperature
• Good heat and chemical resistance
• Low toxicity

• High reactivity above activation temperature

• Broad range of latency • Excellent adhesive characteristics
Imidazoles • Low exothermic curing • High heat and chemical resistance
• Accelerator for DICY

• Long latency • Good balance of physical properties

Modified aliphatic amines • Low to medium activation temperature • Moderate to high heat and chemical resistance
• High reactivity above activation temperature
• Fast green-strength development
• (Co-)Accelerator for DICY

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Evonik‘s epoxy curing agent portfolio for 1K epoxy adhesives

Modified alphatic amines Dicyandiamide Imidazoles

Ancamine® Curezol®
2014AS 2MZ Azine

Longer latency
Longer latency
Ancamine®
Lowest activation temp. 2441 Dicyandiamide
Ancamine® Lower activation temp. Higher heat resistance
Amicure® CG-1200G
2337S
Ancamine® Amicure® CG-1400F
Lower use level
2014FG Good latency
Low activation temperature

Ancamine® Imicure®
2442 EMI-24

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 Evonik’s thermo-latent curing agents for low
temperature 1K epoxy adhesive applications

Ancamine® 2014 AS/FG

®
Ancamine 2337S
Ancamine® 2441

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Product positioning of thermo-latent curing agents for low temperature 1K
epoxy adhesive applications

Type DICY/Accelerators Imidazoles Modified aliphatic amines Solid Adducts

Onset
Down to ~120°C Down to ~80°C Down to ~70°C Down to ~100°C
Temperature
Shel-life @
> 1 month > 1 months > 3 months > 3 months
40°C
✓ Adjustable onset ✓ Large spectrum of ✓ Spectrum of low onset ✓ Low onset temperature
Advantages temperature reactivities temperatures ✓ Good balance of physical
✓ Good balance of physical ✓ Low onset temperature ✓ Good balance of physical properties
properties ✓ Excellent adhesive properties ✓ Good heat and chemical
✓ Good heat and chemical characteristics ✓ Good heat and chemical resistance
resistance ✓ High heat and chemical resistance
✓ Labelling resistance ✓ Labeling
✓ Labeling
- Moderate to short shelf-life - Higher use levels (sole - Higher use levels (sole
Drawbacks - Moderate to short shelf-life (trade off reactivity vs shelf- curing agents) curing agents)
(trade off reactivity vs shelf- life) - Pricing - Pricing
life) - In some cases labeling
- Pricing

16
Evonik’s thermo-latent curing agents for low temperature 1K epoxy adhesive
applications - Overview
Ancamine® 2337S Ancamine® 2014 AS Ancamine® 2014 FG Ancamine® 2441
Appearance Light yellow powder White powder White powder White powder
Particle Size D90 [µm] 10 36 6 10
Amine Value [mg KOH/g] 260 184 184 230
Activation temperature [°C] 71 75 75 100
Sole Curing Agent
Use level [PHR] 50 28 28 20
DSC Onset [°C] 72 109 109 99
Tg (30’ @ 120°C) [°C] 71 77 85 114
Shelf-life @ 42°C [weeks] >4 11 4 > 12
Accelerator for DICY
Use level [PHR] 10* 5 5 5
DSC Onset [°C] 75 / 133 133 133 110
Tg (30’ @ 140°C) [°C] 116 110 118 147
Shelf-life @ 42°C [weeks] >8 > 12 > 12 > 12
* in combination with Ancamine 2014AS/FG or 2441

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Application as sole curing agents
Reactivity and Shelf-life
Ancamine Ancamine Ancamine Ancamine
2337S 2014AS 2014FG 2441
LER (EEW 190) 100 100 100 100
Ancamine 2337S 50 - - -
Ancamine 2014AS - 28 - -
Ancamine 2014FG - - 28 - °C
Ancamine 2441 - - - 20
Fumed Silica 2 2 2 2
Excellent balance of low activation
109 109
114 temperatue and shelf-life
100 99
85
78
72 71

✓
50

20
11 °C

Ancamine 2337S Ancamine 2014AS Ancamine 2014FG Ancamine 2441

Onset Temperature [°C] Tg [°C] after 30 min @ 120°C
Moderate to high Tg
Viscosity Increase (4 weeks @ 42°C) [%]

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Application as sole curing agents
Lap Shear Strength Development
Ancamine Ancamine Ancamine Ancamine
2337S 2014AS 2014FG 2441
LER (EEW 190) 100 100 100 100
Ancamine 2337S 50 - - -
Ancamine 2014AS - 28 - -
Ancamine 2014FG - - 28 -
Ancamine 2441 - - - 20
Fumed Silica 2 2 2 2

11.5 High adhesive strength

9.1
8.5
7.7
7.2
6.2 6.6
6.1
5.2
4.2
3.6

1.5

Ancamine 2337S Ancamine 2014AS Ancamine 2014FG Ancamine 2441

LLS after 30 min @ 80°C [MPa] LLS after 30 min @ 100°C [MPa]

LLS after 30 min @ 120°C [MPa]

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Application as Accelerator for DICY
Reactivity and Shelf-life
Ancamine Ancamine Ancamine Ancamine
2337S 2014AS 2014FG 2441
LER (EEW 190) 100 100 100 100
Amicure CG 1200G 6 6 6 6
Ancamine 2337S 10 - - -
Ancamine 2014AS 4 5 - - °C
Ancamine 2014FG - - 5 -
Ancamine 2441 - - - 5
Fumed Silica 2 2 2 2 High acceleration for DICY and long
shelf-life
133 136
127 127
116 118
110 110

°C
✓
20
5 5 5

Ancamine 2337S Ancamine 2014AS Ancamine 2014FG Ancamine 2441 Moderate to high Tg
Onset Temperature [°C] Tg [°C] after 30 min @ 140°C
Viscosity Increase (4 weeks @ 42°C) [%]

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Application as Accelerator for DICY
Lap Shear Strength Development
Ancamine Ancamine Ancamine Ancamine
2337S 2014AS 2014FG 2441
LER (EEW 190) 100 100 100 100
Amicure CG 1200G 6 6 6 6
Ancamine 2337S 10 - - -
Ancamine 2014AS 4 5 - -
Ancamine 2014FG - - 5 -
Ancamine 2441 - - - 5
Fumed Silica 2 2 2 2

17.3 17.0
High adhesive strength
15.0 15.3
13.0 13.2

10.5 10.8

5.8
4.2
2.6
0.4

Ancamine 2337S Ancamine 2014AS Ancamine 2014FG Ancamine 2441

LSS after 30 min @ 100°C [MPa] LSS after 30 min @ 120°C [MPa]
LSS after 30 min @ 140°C [MPa]

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Application as Accelerator for DICY
Green Strength development after Induction cure
Formulation
Components A B
LER (EEW 190) 87,5 87,5
CTBN modified resin 25 25
DICY 7 7
Ancamine 2014AS 10 -
Ancamine 2337S 12,5 12,5
Ancamine 2441 - 10
Filler 40 40
Fumed Silica 2 2
7.3
High Green-Strength after 4s induction cure
(1s ramp + 3s hold) within 10 min @ RT
4.1
3.6

2.2

A B

LSS after 4s @ 190°C + 10 min @ RT [MPa]

LSS after 4s @ 205°C [MPa] + 10 min @RT [MPa]

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Application as Accelerator for DICY
LSS retention after induction + post-cure
Formulation
Components A B
LER (EEW 190) 87,5 87,5
CTBN modified resin 25 25
DICY 7 7
Ancamine 2014AS 10 -
Ancamine 2337S 12,5 12,5
Ancamine 2441 - 10
Filler 40 40
Fumed Silica 2 2
9 8.8
High adhesive strength after
7.2 6.9
induction (4s) + post cure
(30 min @150°C)
4.5
• at ambiet temperature
2.3
• at elevated temperature
• after aging (hot water)
A B
LSS @ RT [MPa]
LSS @ 150°C [MPa]
LSS @ RT after aging in water (7d @ 55°C) [MPa]

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 Summary

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Evonik’s thermo-latent curing agents for low temperature 1K epoxy adhesives

Key Advantages
▪ Long shelf-life
▪ Low activation temperature
▪ Rapid reactivity above activation temperature
▪ Improved Green-Strength capabilities
▪ High adhesive strength

Potential Applications:
• Structural adhesives
• Automotive & Transportation
• Aerospace & Defense
• Electronics
• Industrial Manufacturing We deliver everything you need to improve productivity and energy efficiency

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Sounds interesting? We can support you?
Get in touch with us!

Discover more on your own Get in contact with the local expert
Dr. Sebastian Clermont
Technical Manager EMEA

Phone +49 2365 49 86785

sebastian.clermont@evonik.com

Pritesh Patel Ph.D.

Marketing Director North America

Phone +1 610 573 5292 pritesh.patel@evonik.com

Phoebe Xu
Product Finder Marketing Manager Asia
crosslinkers.evonik.com/en/product-finder
Phone +86 21 6119 2003 phoebe.xu@evonik.com
Product Page
ancamine.com amicure.com imicure.com

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