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

▶
high performance biopolymers
SMART_READER_LITE
LIVE PREVIEW

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

Nov 06, 2022 144 likes •388 views

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

slide-1
SLIDE 1

1

High Performance Biopolymers

HiperBioPol

slide-2
SLIDE 2

2

Mw = 10900 to 60800 g/mol Mw > 2 x 106 g/mol Repeat units ~ 105 Repeat units ~ 103

slide-3
SLIDE 3

Aachen Maastricht Institute for Biobased Materials 3

weak Van der Waals forces strong hydrogen bonding

Secondary intearctions

Mw > 2000000 g/mol Mw = 10900 to 60800 g/mol

slide-4
SLIDE 4

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

Fiber direction Transverse direction

slide-5
SLIDE 5

5

UHMWPE 90wt% of decalin to spin 10wt% of polymer Kevlar / PPTA 90wt% of conc H2SO4 to spin 10wt% of polymer Solvent recovery plant

slide-6
SLIDE 6

Bio-reactor operational at room temperature

1Jan C.M. van Hest and David A. Tirrell, Chem. Commun., 2001, 2Foo et al., Applied Physics A, 2006

K+ (10-3%) Ca2+ (10-3%) H2O (%)

30.2 17.7 75 29.5 46.0 74 33.3 59.7 74 74 Gel-sol state pH 5.0 Gel state pH 5.2 Gel state pH 6.9 Gel state pH 5.6

  • Different ions
  • Change in pH
  • β-sheet formation

Bio-spinnerette

  • Water as solvent

PPS-30, June 8-12, 2014, Cleveland, Ohio, USA

slide-7
SLIDE 7

Aachen Maastricht Institute for Biobased Materials 7

Aliphatic polyamides

slide-8
SLIDE 8

nylons (PA) and H-bonding

  • nylon x,y:
  • 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

N CH

x

H C O N H CH

y-2

C O

n 2 2

slide-9
SLIDE 9

Origin of the Brill transition

Bunn et al. 1947 ; Rastogi et al. 2004; Vinken et al. 2008

PA66 PA46 intrasheet intersheet intersheet intrasheet

slide-10
SLIDE 10

Origin of the Brill transition and aqueous solubility

Bunn et al. 1947 ; Rastogi et al. 2004; Vinken et al. 2008

intrasheet intersheet PA66 PA46 intersheet intrasheet PA46

slide-11
SLIDE 11

Origin of the Brill transition and aqueous solubility

Bound water αN αC βN βC Mobile water

Rastogi et al. 2004; Vinken et al. 2008; Deshmukh et al. 2013

PA46

slide-12
SLIDE 12

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

slide-13
SLIDE 13

Cooling in water assisted processing of polyamide 6

5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 40 60 80 100 120 140 160 180 200 220

d-spacing [Å] Temperature [°C] Int

5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 40 60 80 100 120 140 160 180

d-spacing [Å] Temperature [°C] Int

Parodi et al. 2017

PA6 degassing H2O H2O (optional)

from melt from H2O

220°C 240°C 180°C 180/220°C

0.17°C/s

slide-14
SLIDE 14

Amide shielding by trapped water

Vinken et al. 2008; Harings et al. 2009

slide-15
SLIDE 15

Amide shielding by trapped water

Vinken et al. 2008; Harings et al. 2009

slide-16
SLIDE 16

Water and ion assisted processing of polyamide 46

Foo et al. Harings et al. 2009, 2012, Deshmukh 2013

1M LiI 8M LiI

F- > PO4

  • > SO4

2- > CH3COO- > Cl- > Br- > I- > SCN-

(CH3)4N+ > (CH3)2NH2+ > NH4

+ > K+ > Na+ > Cs+ > Li+ > Mg+ > Ca2+ > Ba+

protein stabilization protein destabilization

slide-17
SLIDE 17

Additional degrees of freedom: ions

2D 7Li{1H} HETCOR spectrum

Harings et al. 2012; 2018

Extended X-ray Absorption Fine Structure

slide-18
SLIDE 18

Additional degrees of freedom: ions

Harings et al. 2012

MPa

PA46 degassing H2O/Li+/I- H2O as extruded washed + ions washed melt melt 310°C 330°C 270°C 310°C + ions 310°C 330°C 240°C 240°C washing + ions melt

slide-19
SLIDE 19

19

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

  • riented structures, (ii) molecular mixing upon blending, and (iii) ultimate

dispersion of water dispersed functional (nano-)fillers; three processes severely challenged in conventional melt-processing. Jules Harings WP1

slide-20
SLIDE 20

20

The objective of this WP is to do theoretical modelling on water uptake in the polyamides and phase stability during synthesis/processing

  • f

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. WP2 Remco Tuinier

slide-21
SLIDE 21

21

The

  • bjective
  • f

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. WP3 Frank Bergman

slide-22
SLIDE 22

22 Work Package 1

  • J. Harings (WPL, UM)

1 FTE Memb (PD 40 months) 1 FTE Memb (Tech 4 months)

  • R. Tuinier (ProSup, TU/e)
  • L. Balzano (ProSup, DSM)

Work Package 2

  • R. Tuinier (WPL, TU/e)

1 FTE Memb (PhD 4 years)

  • J. Harings (ProSup, UM)
  • K. Wilsens (ProSup, UM)
  • L. Balzano (ProSup, DSM)

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 3

  • F. Bergman (WPL, DSM)
  • H. Oevering (Memb, DSM)

Vacancies (Memb, DSM)

  • J. Harings (ProSup, UM)
  • K. Wilsens (ProSup, UM)
  • R. Tuinier (ProSup, TU/e)

Work Package 4

  • H. Oevering (WPL, DSM)
  • J. Harings (ProSup, UM)
  • K. Wilsens (ProSup, UM)
  • F. Bergman (ProSup, DSM)
slide-23
SLIDE 23

23

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

  • ther workpackages. At first T.06.04.01 will be executed by (i) gathering input data
  • f 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

  • f

the developed polycondensates and process and assess the total benefit of the developed concepts. WP4 Henk Oevering

slide-24
SLIDE 24

Aachen Maastricht Institute for Biobased Materials 24

High level timelines and interdependencies of work packages

2018 2019 2020 2021 Piloting WP 1 WP 2 WP 3 WP 4