Toughen up your coating with B-Tough TM

Transcription

1 Toughen up your coating with B-Tough TM Epoxy functional dimer technology for epoxy coatings European Coatings Conference February 28-29, 2012 Berlin

2 Content Introduction to toughening Introduction to dimer acids in epoxy systems Prove of concept Results of B-Tough C2 TM versus conventional technologies Conclusions

3 Introduction to toughening Introduction to dimer acids in epoxy systems Prove of concept Results of B-Tough C2 versus conventional technologies Conclusions

4 What is toughness? Glass is hard but too brittle A mattress is flexible but too soft

5 What is toughness? = impact resistance

6 And what if a material is not tough? Hard and non-flexible materials are vulnerable to cracking Cracks are caused by: impact/collision exposure to severe conditions temperature UV radiation/sun light chemicals (salt water)

7 Why are cracks bad? Cracks undermine the protective effect of coatings

8 Why are cracks bad? Cracks undermine structural integrity

9 Epoxy toughened systems Epoxy toughening is a well-known concept in several epoxy applications Adhesives: Construction Aerospace Automotive Electronics Hard disk Conductors Motherboard Assembly Windmill

10 Conventional technologies used for toughening Type Non reactive block copolymer Silicon modified toughener (reactive) Elastomer toughener (reactive) Viscosity [mpa.s] Remarks Present as individual (separate) particles in epoxy matrix Silicon core, epoxy functional shell, chemically bonded to epoxy matrix, high viscosity Epoxy functionalised CTBN rubber, very high viscous

11 Market trends VOC reduction Low VOC, high solid trend Unions & Occupational Safety & Health authorities Reduce time & costs Faster cure Wider over coating interval Low temperature cure Easy to apply Higher performance Longer lifetime New functionalities: e.g. self cleaning

12 Croda offerings to the market Pripol TM Dimer acid Polyamide curative Epoxy modification Priamine TM Dimer diamine Dimer Diamine curative B-Tough TM Toughening agent Epoxy modification Flexibility hardness high VOC Low viscous Flexibility Low VOC Flexibility and Hardness year

13 Content Introduction to toughening Introduction to dimer acids in epoxy systems Prove of concept Results of B-Tough C2 versus conventional technologies Conclusions

14 Why? Dimer acid use in epoxy resins Dimer acid use in epoxy resins Brings flexibility (vibration/stress absorption) Enhances hydrophobicity, weatherability and compatibility with organic matrices (tar, hydrocarbon resins) Large hydrocarbon part (C 36 ) Hydrophobic Hydrolytic resistance of derivatives Affinity for non-polar matrices and surfaces Irregular non-crystalline structure Flexibility Low T g Flow, wetting HOOC COOH

15 Dimer acid use in epoxy resins Dimer acid technology traditionally used in epoxy resins In polyamide curatives In modified epoxies; flexibility at cost of hardness though C H 3 C H 3 brittle Mandrel Flex [mm] flexible Epikote 828/ref. Dimer acid modified epoxy Hardness [s] C H 3 O O O O H O O O O H C H 3 C H 3 C H 3 Mandrel Flex König hardness O O O O

16 Dimer technology for impact modification Low glass transition temperature and low polarity of dimer acid makes it suitable for flexibilisation Dimer acid too small as soft segment (M w 580) for phase separation B-Tough epoxy functional dimer technology allows incorporation of larger molecular weight soft segments Potentially resulting in phase separated morphology Resulting in better toughening performance etc.

17 Modification of rigid polymers with apolar soft segments A special way of impact modification Crystalline or high-t g amorphous hard segments Large low-t g amorphous soft segments flock together, driven by polarity difference, forming large domains that provide impact strength. Copolymer, chemically linked, therefore no stability issues.

18 Phase separated morphology Soft segments form rubbery particles in hard epoxy matrix Results in impact strength Rubbery particles restrict crack growth Energy of crack is absorbed by the rubber By plastic deformation, shear banding, cavitation Toughness: reducing crack growth while maintaining a hard matrix For hardness and good high temperature performance Toughness requires 2-phase structure

19 Additional advantages Due to the incorporation of B-Tough in the epoxy the moisture diffusion will be reduced as the dimer technology is extremely hydrophobic B-Tough can be added as additive to the system No volatile toxic or smelly monomers Not susceptible to thermal or oxidative degradation Very low glass transition temperatures Easy to formulate: low viscous

20 Epoxy functionalised toughening agent B-Tough C2 Typical values Product code EEW Typical [g/eq] Rubber content [%] 25 C Typical [mpa.s] B-Tough C Viscosity much lower than many conventional tougheners easier to formulate with B-Tough Compatible enough to react, phase separate during cure

21 Explanation rubber content B-Tough C2 contains 40% rubber phase: Epoxy-part: 20% Rubber -part: 40% B-Tough C2 Benzyl alcohol-part: 40% So 5% rubber requires 5 = 12.5 % w/w B-Tough C Example: if 100 g contains 5% rubber, it contains 12,5 g B-Tough C2

22 Content Introduction to toughening Introduction to dimer acids in epoxy systems Prove of concept Results of B-Tough C2 versus conventional technologies Conclusions

23 Toughening in coating systems Liquid vs. solid epoxy resin, various hardeners EPIKOTE 828 Epoxy toughening agent: 5% rubber phase Hardener: Ancamide 3201: polyaminoamide adduct (previously known as SIQ 2201) Ancamide 2386 : modified amidoamine Formulated to 80% solids with xylene/butanol (4/1) EPIKOTE 1001 Epoxy toughening agent: 5% rubber phase Hardener: Ancamide 3201: polyaminoamide adduct (previously known as SIQ 2201) Ancamide 2386 : modified amidoamine Formulated to 70% solids with xylene/butanol (4/1) Solid epoxy 1001 requires more solvent than liquid epoxy 828

24 Method/formulation Preparation Formulation (in parts by weight): Epoxy resin Epikote B-Tough C2 23 Solvent 44 Xylene/Butanol (4:1) Curing agent Ancamide Properties Solid content 80% C 150 mpa.s Initial Rubber phase 5%

25 Toughening in coating systems Evaluation Test conditions of the coating 1 25 C 100µ wet Mechanical properties: Flexibility (Mandrel) Hardness König Impact at 25 /4 / -25 C Direct Indirect Chemical resistance Chemicals Salt spray

26 Impact of varying amount of B- Tough C2 on hardness and flexibility Impact of of B-Tough C2 on hardness and flexibility Epikote 828, cured wwith ith SIQ 2201 (Ancamide 3201), curing 11 w eek at at 25 C brittle Mandrel flexibility [mm] Mandrel flexibility [mm] flexible Ref (0%) 2,5% 5,0% 7,5% 0 Ref (0%) Percentage 2,5% B-Tough C2 5,0% (active a.k.a. rubber 7,5% part) Percentage B-Tough C2 Flexibility Hardness König hardness [s] Flexibility 100 Hardness König hardness [s] Higher load of B-Tough C2 improves flexibility; hardness drops only little bit

27 Impact of varying amount of B- Tough C2 on impact resistance Impact resistance for varying percentages of B-Tough C2 Epikote 828, cured w ith SIQ 2201 (Ancamide 3201), curing 1 w eek at 25 C Impact resistance [kg.cm] Ref (0%) 2,5% 5,0% 7,5% Percentage B-Tough C2 Higher load of B-Tough C2 improves impact resistance for both high and low temperatures Direct impact (25 C) Indirect impact (25 C) Direct impact (-25 C) Indirect impact (-25 C) Freedom of formulation due to ease of mixing

28 Mandrel flexibility/hardness 5% rubber phase, B-Tough C2, Ancamide 3201 brittle 35 Epikote with hardener Ancamide Mandrel Flex [mm] Hardness [s] flexible E1001/ref. E828/ref. 828 with B-Tough C2 (5%) Epoxy functionalised toughening agent Mandrel Flex (100 µm) König hardness Allows change from solid to liquid resin for VOC reduction Hardness of 828 system, non-brittle, with flexibility of 1001 system

29 Impact resistance 5% rubber phase, B-Tough C2, Ancamide 3201 Impact resistance [kg.cm] E1001/ref. Epikote with hardener Ancamide E828/ref. 828 with B-Tough C2 (5%) Direct impact (25 C) Indirect impact (25 C) Indirect impact (4 C) Epoxy functionalised toughening agent

30 Mandrel flexibility/hardness 5% rubber phase, B-Tough C2, Ancamide 2386 brittle 35 Epikote with hardener Ancamide Mandrel Flex [mm] Hardness [s] 0 0 flexible E1001/ref. E828/ref. 828 with B-Tough C2 (5%) Epoxy functionalised toughening agent Mandrel Flex König hardness Coatings with this hardener are already flexible But toughening agent does improve impact strength (next slide)

31 Impact resistance 5% rubber phase, B-Tough C2, Ancamide 2386 Impact resistance [kg.cm] E1001/ref. Epikote with hardener Ancamide E828/ref. 828 with B-Tough C2 (5%) Epoxy functionalised toughening agent Direct impact (25 C) Indirect impact (25 C) Indirect impact (4 C) Indirect impact (-25 C)

32 So the B-Tough C2 technology proved to work. How about performance versus conventional technologies?

33 Content Introduction to toughening Introduction to dimer acids in epoxy systems Prove of concept Results of B-Tough C2 versus conventional technologies Conclusions

34 Viscosity of toughened mixtures Toughening agent Viscosity of pure toughening agent Dynamic viscosity of mixture; Viscosity increase vs reference; Formulation: [% rubber on formulation ] [mpa.s] after C [mpa.s] after C [%] Reference B-Tough C Non-reactive block copolymer Silicon modified Elastomer modified *) All formulations: Epikote 828 as resin Xylene/butanol (4/1), 10%, as solvent Ancamide 3201 (SIQ 2201) as curing agent

35 Mandrel flexibility/hardness 5% rubber phase, against alternative toughening technologies Epikote 828 with hardener Ancamide brittle Mandrel Flex [mm] Hardness [s] 0 0 flexible 828/ref. B-Tough C2 non reactive block copolymer silicon modified elastomer modified Epoxy toughening agent Mandrel Flex König hardness

36 Impact resistance 5% rubber phase, against alternative toughening technologies Impact resistance [kg.cm] /ref. Epikote 828 with hardener Ancamide B-Tough C2 non reactive block copolymer silicon modified elastomer modified direct 25 C indirect 25 C indirect -25 C Epoxy toughening agent

37 Impact of curing temperature on hardness and flexibility Impact of B-Tough C2 on hardness and flexibility after curing at different temperatures for 1 week Epikote 828, cured w ith SIQ 2201 (Ancamide 3201) brittle Mandrel flexibility [mm] König hardness [s] 0 0 flexible Ref (0%), 5 C 5%, 5 C Ref (0%), 25 C 5%, 25 C Ref (0%), 35 C 5%, 35 C Percentage B-Tough C2 and curing temperature Flexibility König hardness At low temperature, curing remains slow At high(er) temperatures, trend is similar to that at room temperature: B-Tough C2 increases flexibility, at the same time remains hardness

38 Impact of curing temperature on impact resistance Impact resistance after curing at different temperatures for 1 week Epikote 828, cured with SIQ 2201 (Ancamide 3201) Impact resistance [kg.cm] Ref (0%), 5 C Too sticky to measure due to low temp 5%, 5 C Ref (0%), 25 C 5%, 25 C Ref (0%), 35 C 5%, 35 C Direct impact (25 C) Indirect impact (25 C) Direct impact (-25 C) Indirect impact (-25 C) Percentage B-Tough C2 and curing temperature Similar trend at higher temperature as seen at room temperature: B-Tough C2 improves impact resistance significantly at only 5% addition.

39 Taber test results Coating layer [mm] Weight loss [mg] Reference % B-Tough C Non-reactive block copolymer Silicon modified toughening agent Elastomer modified toughening agent ISO : 1000 cycles, C17 wheel (medium abrasive)

40 Content Introduction to toughening Introduction to dimer acids in epoxy systems Prove of concept Results of B-Tough C2 versus conventional technologies Conclusions

41 Conclusions Toughen-up the epoxy coating with epoxy functionalised toughening agent B- Tough C2 1. B-Tough C2 allows to achieve the flexibility of Epikote 1001 (solid epoxy) based solvent coatings in Epikote 828 (liquid epoxy) based coatings, with the hardness of an Epikote 828 coating. 2. B-Tough C2 allows improvement of flexibility and whilst maintaining the surface hardness. 3. B-Tough C2 also works well at low temperatures. Additional features of B-Tough C2: Low viscous, ease of handling. Thermal and oxidative stability guaranteed.

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