High Performance Biopolymers HiperBioPol 1 Repeat units ~ 10 5 Mw - PowerPoint PPT Presentation

High Performance Biopolymers HiperBioPol 1

Repeat units ~ 10 5 Mw > 2 x 10 6 g/mol Repeat units ~ 10 3 Mw = 10900 to 60800 g/mol 2

Secondary intearctions weak Van der Waals forces Mw > 2000000 g/mol strong hydrogen bonding Mw = 10900 to 60800 g/mol Aachen Maastricht Institute for Biobased Materials 3

Transverse direction Fiber direction Carothers and Hill; JACS 1932 , 54, 1579 “ picture(d) a perfectly oriented fiber as consisting essentially of a single crystal in which long molecules are in ordered array parallel with the fiber axis” “ In actual fibers a considerable number of the molecules fail to identify themselves completely with [the] perfectly ordered structure” chain folded crystals (isotropic) extended chain crystals E = 2-3 GPa E = ~220 GPa

UHMWPE 90wt% of decalin to spin 10wt% of polymer Solvent recovery plant Kevlar / PPTA 90wt% of conc H 2 SO 4 to spin 10wt% of polymer 5

Bio-reactor operational at room temperature 33.3 59.7 74 74 Gel state • Different ions pH 5.2 Gel-sol 29.5 state pH 46.0 • Change in pH 5.0 74 • β-sheet formation Gel state K + (10 -3 %) pH 6.9 Gel state pH 5.6 30.2 Ca 2+ (10 -3 %) • Water as solvent 17.7 H 2 O (%) 75 Bio-spinnerette 1 Jan C.M. van Hest and David A. Tirrell, Chem. Commun., 2001, 2 Foo et al., Applied Physics A, 2006 PPS-30, June 8-12, 2014, Cleveland, Ohio, USA

Aliphatic polyamides Aachen Maastricht Institute for Biobased Materials 7

nylons (PA) and H-bonding O O H H • nylon x,y: N CH C N CH C 2 2 x y-2 n • crystal structure from H-bonded sheets connected via v.d. Waals interactions • H-bonding between N-H and C=O • change H-bond density by - changing aliphatic parts - changing chemical structure via copolymers (piperazine) Atkins et al., Macromolecules , 1992 , 25, 917-924

Origin of the Brill transition intersheet intrasheet intersheet intrasheet PA66 PA46 Bunn et al. 1947 ; Rastogi et al. 2004 ; Vinken et al. 2008

Origin of the Brill transition and aqueous solubility intersheet intrasheet intersheet intrasheet PA66 PA46 PA46 Bunn et al. 1947 ; Rastogi et al. 2004 ; Vinken et al. 2008

Origin of the Brill transition and aqueous solubility Bound water α N α C β N β C Mobile water PA46 Rastogi et al. 2004 ; Vinken et al. 2008 ; Deshmukh et al. 2013

Superheated state of water; a good solvent Adjacent re-entry with 4 repeat units per stem, identical to single crystals from organic solvents. Vinken et al. 2008 ; Atkins et al. 1992

Cooling in water assisted processing of polyamide 6 from melt from H 2 O Int Int 220 180 200 160 180 140 Temperature [°C] 0.17 °C/s 160 Temperature [°C] 120 140 120 100 100 80 80 60 60 40 40 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 d-spacing [Å] d-spacing [Å] Parodi et al. 2017 PA6 degassing H 2 O H 2 O (optional) 220 °C 240 ° C 180 °C 180/220 ° C

Amide shielding by trapped water Vinken et al. 2008 ; Harings et al. 2009

Amide shielding by trapped water Vinken et al. 2008 ; Harings et al. 2009

Water and ion assisted processing of polyamide 46 8M LiI 1M LiI protein stabilization F - > PO 4 - > SO 4 2- > CH 3 COO - > Cl - > Br - > I - > SCN - (CH 3 ) 4 N + > (CH 3 ) 2 NH 2+ > NH 4 + > K + > Na + > Cs + > Li + > Mg + > Ca 2+ > Ba + protein destabilization Foo et al. Harings et al. 2009 , 2012, Deshmukh 2013

Additional degrees of freedom: ions Extended X-ray Absorption Fine Structure 2D 7 Li{ 1 H} HETCOR spectrum Harings et al. 2012; 2018

Additional degrees of freedom: ions PA46 degassing H 2 O/Li + /I - H 2 O melt 310 °C 330 ° C 270 °C 310 ° C + ions 310 °C 330 ° C 240 °C 240 ° C as extruded washed washing melt MPa melt + ions + ions washed Harings et al. 2012

WP1 Jules Harings Technically exploit novel, water and ion induced control in solution processing and structure evolution of aliphatic and aliphatic-aromatic polyamides with enhanced mechanical and functional performance. We will use water molecules to mediate amide hydrogen bonding, ensuring (i) highly oriented structures, (ii) molecular mixing upon blending, and (iii) ultimate dispersion of water dispersed functional (nano-)fillers; three processes severely challenged in conventional melt-processing. 19

WP2 Remco Tuinier The objective of this WP is to do theoretical modelling on water uptake in the polyamides and phase stability during synthesis/processing of hydrophobic/hydrophilic balanced polycondensates . Considering that water promotes enzymatic degradation and influences the mechanical response of the material, the study will also be used to guide the design of the molecular configuration of polycondensates. Thus providing guidance to WP1, 3 and 4. 20

WP3 Frank Bergman The objective of this WP is to map the relationship between polymer compositions – polymer properties of hydrophobic biobased polycondensates . Guidance from WP2 on the expected phase stability during synthesis/processing will be incorporated in this WP. The WP therefore aims to further optimize synthetic procedures of the developed polycondensates, scale-up > 30 kg scale and validate the performance and processing. 21

Project Management Team S. Rastogi (PL+PartCoord; UM) E. Staring (Managing Director; InSciTe) M. Rijkers (Program Manager, InSciTe) F. Bergman (PartRep+PartCoord+ WPL; DSM) J. Harings (WPL; UM) R. Tuinier (PartCoord+WPL; TU/e) Work Package 1 Work Package 2 Work Package 3 Work Package 4 R. Tuinier (WPL, TU/e) F. Bergman (WPL, DSM) H. Oevering (WPL, DSM) J. Harings (WPL, UM) 1 FTE Memb (PhD 4 years) H. Oevering (Memb, DSM) J. Harings (ProSup, UM) 1 FTE Memb (PD 40 months) J. Harings (ProSup, UM) Vacancies (Memb, DSM) K. Wilsens (ProSup, UM) 1 FTE Memb (Tech 4 months) K. Wilsens (ProSup, UM) J. Harings (ProSup, UM) F. Bergman (ProSup, DSM) R. Tuinier (ProSup, TU/e) L. Balzano (ProSup, DSM) K. Wilsens (ProSup, UM) L. Balzano (ProSup, DSM) R. Tuinier (ProSup, TU/e) 22

WP4 Henk Oevering WP4 of this project will address Life Cycle Assessment of the synthesis to processing of the polymers. This workpackage will be executed in parallel to the other workpackages. At first T.06.04.01 will be executed by (i) gathering input data of the relevant commercial reference systems (ii) compare with the intended concepts in WP.06.01, and WP.06.03 and (iii) report on the LCA end result. T.06.04.02 will lift the LCA and economical evaluation to the next level by incorporating in the analysis the end-use application of the developed polycondensates and process and assess the total benefit of the developed concepts. 23

High level timelines and interdependencies of work packages 2018 2019 2020 2021 WP 1 WP 2 WP 3 WP 4 Piloting Aachen Maastricht Institute for Biobased Materials 24