C. Croutxé-Barghorn M. Retailleau, A. Ibrahim, X. Allonas

Transcription

1 C. Croutxé-Barghorn M. Retailleau, A. Ibrahim, X. Allonas

2 Free radical photopolymerization Liquid state Glassy state PI PI PI PI PI hv, RT, few seconds fast, solvent-less and eco-friendly PI : photoinitiator Chain growth polymerization: Incomplete conversion : vitrification Non homogenous polymer network Alternative Step growth polymerization + Chain growth polymerization

3 Michael addition and photopolymerization Two-stage photopolymerization ne-click : nucleophile : diacrylate : thiol -C bond : hν C-C bond cleophile + acrylates (excess) + catalyst (+ ΔT) Stage 1: self-limiting click Michael addition (step growth) Stage 2: Photopolymerization (chain growth) - Dynamically controlled polymerization - Homogeneous network - Easily tunable material Literature 1997 : carbon-michael + hv 2012 : thiol-michael + hv 2015 : aza-michael + hv Pavlinec, J.; Moszner, N., J. Appl. Polym. Sci. 1997, 65 (1), Nair, D. P.; Cramer, N. B.; Gaipa, M. K.; Matherly, E. M.; McLeod, R. R.; Shandas, R.; Bowman, C. N., Adv. Funct. Mater. 2012, 22 (7), Retailleau, M.; Ibrahim, A.; Croutxé-Barghorn, C.; Allonas, X., W A Gonzalez, G.; Fernandez-Francos, X.; Serra, A.; Sangermano, M.; Ramis, X., Polym. Chem. 2015, 6, ,

4 Wu; Liu, Y.; Chen, L.; He; Chung, T. S.; Goh, S. H., Macromolecules 2005, 38 (13), Mather, B. D.; Viswanathan, K.; Miller, K. M.; Long, T. E., Prog. Polym. Sci. 2006, 31 (5), Retailleau, M.; Ibrahim, A.; Croutxé-Barghorn, C.; Allonas, X., W A Aza-Michael addition Properties: - Absence of catalyst, - Primary amines can react with two electrophiles R 2 Double-Click chemistry AZ 1 H EWG + 2 H EWG aza-michael + hν EWG: Electron Withdrawing Group R AZ 2 + H AZ 1 + AZ 2 EWG Simultaneous or sequenced?

5 Kinetics of aza-michael addition Ratio of consumed and generated species (%) Modeling 2 :C=C ratio of 1: H-NMR monitoring 1,5-diaminopentane (DP) k AZ1 = ± H 2 N + 2 M 1. s 1 k AZ2 = ± M 1. s 1 ethoxylated bisphenol A diacrylate (EBAD) Two-stage mechanism AZ 1 / AZ 2 Possibility to interpose a hν + b = Acrylates 80 min Time (d) AZ 1 AZ 2 N H 2 N

6 The three-stage concept

7 Three-stage concept Amine, acrylates and photoinitiator

8 Three-stage concept AZ 1 80 min Using kinetics differences 8

9 AZ 1 Three-stage concept hv vercoming vitrification issues 9

10 AZ 1 Three-stage concept hv AZ 2 N N N N N N? N N Progress of AZ 2 in a vitrified media?

11 Conversion (%) Acrylate conversion (%) Proof of concept Acrylate conversion monitoring 100 Stage 2 Conv (%) 78 2 :C=C ratio of 1:4 + I nm P 80 AZ 2 can progress in a vitrified media Light FF Stage 1 Conv (%) Stage 3 25 Conv (%) 91 Light N 80 min 2 min 25 days 0 0,070 0, Time (min) Time (d)

12 AZ 2 : an added value?

13 Benefits of the 3-stage process on T g Photochemical process hv Conversion (%) T g ( C) Conventional two-stage AZ 1 AZ 2 hv Three-stage concept AZ 1 hv AZ 2 AZ 2 : Reduced vitrification 13 - Higher T g

14 Storage Modulus (MPa) Benefits of the 3-stage process on polymer network Storage modulus monitoring AZ 1 + hv Dangling ends broad mechanical transition (ΔT = + 31 C) after hv Temperature ( C)

15 Storage Modulus (MPa) Benefits of the 3-stage process on polymer network Storage modulus monitoring AZ 1 + hv + AZ Narrow mechanical transition (ΔT = + 8 C) after hv 10 days after hv Temperature ( C) Highly homogeneous network Highly responsive to thermal changes

16 Applications

17 Heat Induced SMP Shape Memory Polymers T > T g T < T g Temporary Shape Temporary Shape Permanent Shape A Heat 1- Deformation B Cooling 2- Fixation B Heat 3- Recovery T > T g Key factor: network homogeneity Lendlein, A.; Kelch, S., Angew. Chem. Int. Ed. 2002, 41 (12),

18 Stress Light Induced SMP σ T Cyclic thermomechanical test ε u T g ε p ε ε m R r : shape recovery (SMP's ability to recover the permanent form) R r = R f : shape fixity (SMP's ability to be fixed by mechanical deformation after successive cooling and unloading steps) σ = 0RMPa f = ε u(n) V rec : recovery rate R f (%) R r (%) V rec (%. C -1 ) ε m ε p (N) ε m ε p (N 1) N = nb of cycles V rec = T e T s Shape memory polymers and photopolymerization : ε m R r 95 % 95 % temperature interval of recovery AZ 1 + hν (t = 0 j) ,5 AZ 1 + hν + AZ 2 (t = 25 j) ,0 Thiol-Michael + hv ,9 Higher R f, R r and V rec with the 3-step process based on AZM Sauter, T.; Heuchel, M.; Kratz, K.; Lendlein, A., Polym. Rev. 2013, 53 (1), Retailleau, M.; Ibrahim, A.; Croutxe-Barghorn, C.; Allonas, X., RSC Adv. 2016, 6 (52),

19 Heat Induced SMP Heating 60 C Video slowed down 4 times 19 Retailleau, M.; Ibrahim, A.; Croutxe-Barghorn, C.; Allonas, X., RSC Adv. 2016, 6 (52),

20 Coatings with self-healing properties Reference (only hn) hv AZ 1 + hv + AZ 2 (t) (EBAD) t = 0 d t = 2 d t = 7 d t = 14 d t = 21 d Persoz hardness (s) Vickers hardness (GPa) 15,9 ± 0,4 5,9 ± 0,1 / / / 15,7 ± 0.1 Creep (%) 13,4 ± 0,1 32,2 ± 0,4 / / / 9,8± 0,1 Persoz Hardness (glass) = 420 s Vickers Hardness (glass) = 2-8 GPa 2-step process: Dandling chains not included in the network 3-step process: Dandling chains included in the network Weak mechanical properties Χ Coating Xiao, X.; Xie, T.; Cheng, Y.-T., J. Mater. Chem. 2010, 20 (17), Binder, W. H., Self-Healing Polymers: From Principles to Applications;Wiley: Increased mechanical properties Coating

21 Coatings with self-healing properties Durometer test Diamond tip (diameter : 100 µm) Glass substrate 0,25 N 0,5 N 1,5 N 1,75 N hν 100 μm AZ 1 + hν + AZ 2 Sinha, S. K., Scratching of Polymers: Deformation Mapping and Wear Modeling In Scratching of Materials and Applications, Briscoe, B. J., Ed. Elsevier Science: Increased scratch resistance 21

22 Coatings with self-healing properties 1,5 N Before heating 1 min à 80 C 100 μm Epaisseur ( m) L = 162 μm P = 7,9 μm Largeur ( m) Largeur ( m) Epaisseur ( m) L = 153 μm P = 1,2 μm 2 min à 80 C 4 min à 80 C Epaisseur ( m) L = 136 μm P = 0,7 μm Epaisseur ( m) L = 0 μm P = 0 μm Largeur ( m) Largeur ( m)

23 Conclusion Aza Michael addition and photopolymerization AZ 1 hv AZ 2 ne pot three-step process No vitrification issue Homogeneous network architecture Smart properties

24 Conclusion Aza Michael addition and photopolymerization Impregnated glass-fiber plies AZ 1 Compaction SMP Coatings SM Composites ne pot three-step process No vitrification issue Homogeneous network architecture Smart properties

25 Conclusion Aza Michael addition and photopolymerization Impregnated glass-fiber plies AZ 1 + hv SMP Coatings SM Composites ne pot three-step process No vitrification issue Homogeneous network architecture Smart properties

26 Conclusion Aza Michael addition and photopolymerization Impregnated glass-fiber plies AZ 1 + hv + SMP Coatings SM Composites AZ 2 ne pot three-step process No vitrification issue Homogeneous network architecture Smart properties

27 Conclusion Aza Michael addition and t = 0 s photopolymerization t = 30 s Coatings SM Composites ne pot three-step process No vitrification issue Homogeneous network architecture Smart properties

28 M. Retailleau A. Ibrahim X. Allonas 28

29 5 th European Symposium of Photopolymer Science Mulhouse, France September 3-6,