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Are Ionic Liquids suitable for the Lyocell Spinning Process? · 2017-04-26 · COST Action FP 1205...
Transcript of Are Ionic Liquids suitable for the Lyocell Spinning Process? · 2017-04-26 · COST Action FP 1205...
COST Action FP 1205 Cellulose material properties and industrial
potential
Final Meeting in StockholmMarch 8th, 2017
Herbert Sixta
Are Ionic Liquids suitable for the Lyocell Spinning Process?
No info on regeneration conditions, filmsor fibre mechanical properties
The first paper reporting about theproduction and characterization of IL-based Lyocell fibers
PART 1
ILs as Cellulose Solvents• Cellulose Dissolution• Rheology• Thermal Stability• Toxicity
Ionic liquids(M.P. < 100°)
R.T. ILs(M.P. < RT)
Acid superbaseconjugates
(M.P. > RT)
Phase-SeparableILs
Aqueous OniumElectrolytes
R1 R2 R3
H
1,5-diazabicyclo[4.3.0]non-5-ene (DBN)
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)
7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene (MTBD)
N,N,N,N,NN,-hexamethylphosphorimide triamide (HMPI)
1,2-dimethyl-1,1,4,5,6-tetrahydropyrimidine (DMP)
N,N,N,N,-tetramethylguanidinium (TMG)N N
NH
N N
O
O-
Parviainen, A.; King, A.W.T., Mutikainen, I.; Hummel, M.; Selg, C.; Hauru, L.K.J., Sixta, H.; Kilpelainen, I. ChemSusChem 2013, 6, 2161-2169Lenz. Ber (2005), 84:71-85Lenz. Ber (2006), 86:154-161
Cellulose Dissolving ILs
Chem. Lett. 2012, 41, 987-989; ChemSusChem 2012, 5, 388-391
Amino Acid Ionic Liquid
Dissolution of cellulose (MCC)at 100°C, 10 min:
[N221ME][Ala], KT-β = 1.041 12 wt%[N221ME][Lys], 11 wt%[N221ME][OAc], 7 wt%
[N221ME][Ala]: DMSO = 1:1 (w/w), χIL = 0.25dissolves 22 wt% cellulose at RT!!
Amino group essential to realize high cellulose dissolution->amino group mayinteract with certain parts of cellulose.
N+
ONH2
O
-O
[N221ME][Ala]
N,N,-diethyl-N-(2-methoxyethyl)-N-methyl-ammonium alanine
Dissolution Window
Hauru, L.K.J.et al.. Biomacromolecules 2012, 13, 2896-2905.
KT: Net-basicity Concept
0,0 0,3 0,6 0,9 1,2 1,5-1,0
-0,5
0,0
0,5
1,0
--100
20
[emim]OAc [TMGH]EtCO2
[TMGH]OAc NMMOH2O NMMO2H2O LiCl/DMAc
[Pnnnn] [Rmim]MeOHPO2
[eimH]EtCOO DMAPH]EtCOO [HOC2mim] [EMIM] [BMIM]
[DBNH][OAc]
M.J. Kamlet and R.W. Taft: JACS, 98:2, 377-383 (1976)R.W. Taft and M.J. Kamlet: JACS, 98:10, 2886-2894 (1976)M.J. Kamlet, J-L.M. Abboud, MH: Abraham, R.W.Taft, JOGS, 48, 2877-2887 (1983)
Rheological properties
70 75 80 85 90 95 1000
1
2
3
15k
30k
45k60k75k
20 wt%
13 wt%
[emim][OAc]
Euca-PHKs
-1
[] 0* , P
a.s
Temperature, C
at c
ross
-ove
r
[DBNH][OAc]NMMOxH2O
13 wt%
Cellulose solutions (dopes)
Thermal stability of ILs
Partly unpublished results
50 100 150 200 250 3000
2550
70
80
90
100W
eigh
t per
cent
Temperature, °C
[BMIM][dmp] [AMIM][dmp] [EMIM][OAc] [DBNH][OAc] [TMGH][OAc]
PART 2
Cellulose Coagulation• Diffusion of water• Structure formation• Cellulose gelation
Diffusion of water into the filament
Hauru, L. et al. Soft Matter, 2016, 12, 1487-1495
0 2 4 6 8 10 12 140,6
0,4
0,2
0,0
radial distance from center [µm]de
pth
trave
lled
in b
ath
[m]
0,01
0,05
0,10
0,15
0,20
0,40
0,80
1,00NMMO
20 s40 s60 s90 s
120 s150 s180 s
Water diffusion• fastest for NMMO• slowest for
[emim]OAc
0 2 4 6 8 10 12 140,6
0,4
0,2
0,0
radial distance from center [µm]de
pth
trave
lled
in b
ath
[m]
0,01
0,05
0,10
0,15
0,20
0,40
0,80
1,00[DBNH][OAc]
0 2 4 6 8 10 12 140,6
0,4
0,2
0,0
radial distance from center [µm]de
pth
trave
lled
in b
ath
[m] 0,00
0,05
0,10
0,15
0,20
0,40
0,80
1,00[emim][OAc]
0 5 10 15 20
0,2
0,4
0,6
0,8
1,0
Pene
trat
ion
dept
h (m
)
Extrusion velocity (m/min)
∆· ··
Regeneration depth, ∆ , of a [DBNH][OAc] dope
, 100
1.55 · 10 ⁄
Ve = 0.05 mL/minDR = 10V0 = 63.7 m/min
Rh (LS)
5 wt% 8 wt%
0 5 10 15 200
10
20
30
40
50
60
Tena
city
(cN
/tex)
con
d
Draw ratio
0 wt% water 2 wt% water 5 wt% water
0,1 1 10 1000
200
400
600
800
Rh,
nm
Water content, %
[emim][OAc]
Olga Kuzmina et al. Fibers and Textiles in Eastern Europe 2010, 18, 3 (80), 32-37
13 wt% birch-PHK in[DBNH][OAc]
Anne Michud, Doctoral Dissertation, Aalto University, Finland, p38
Regeneration in water
0 10 20 30 40 50
0
100
200
300Tu
rbid
ity (N
TU)
water (%)
Turbidity
0,1
1
10
100
0 10 20 30 40 50
0
100
200
300Tu
rbid
ity (N
TU)
water (%)
Turbidity
0,1
1
10
100
Complex viscosity
Com
plex
vis
cosi
ty [P
a·s]
0 10 20 30 40 50
0
100
200
300Tu
rbid
ity (N
TU)
water (%)
Turbidity
0,1
1
10
100
tan
Complex viscosity tan
Com
plex
vis
cosi
ty [P
a·s]
3% cotton linters (DP 1975) in [emim][OAc]
M. Hummel, ACS conference, San Diego 2012Le Kim Anh, R. Sescousse, T. Budtova. Cellulose 2012
PART 3
Spinnability• Causes for instability• Effect of MMD
SpinnabilitySpinning solvent
D0[m]
Textr[°C]
DRmax Tenacity[cN tex-1]
[DBNH][OAc] 100 70 7,5 38.5±8.4
NMMO.H2O 100 95 6,2 31.2±6.6[TMGH][OAc] 100 80 2,0 10.9±1.1[emim][OAc] 250 90 2,9 13,9±1.6
[TMGH][OAc] and [emim][OAc] not spinnable.
Spinning solvent
D0[m]
Textr[°C]
DRmax Tenacity[cN tex-1]
[DBNH][OAc] 100 70 7,5 38.5±8.4
NMMO.H2O 100 95 6,2 31.2±6.6[TMGH][OAc] 100 80 2,0 10.9±1.1[emim][OAc] 250 90 2,9 13,9±1.6
Spinning performance
0 20 40 60 80 1000
20
40
60
80
100
D [1
0-11 m
2 /s]
water content [%]
[DBNH]OAc [emim]OAc [TMGH]OAc NMMO
Poorly orientable network of [TMGH][OAc] and [emim][OAc] dopes.Constant diffusion across water contentindicative for gelatineous network.
Solvent diffusion vs. water cont1 2 3 4 5 6 7 8
0
10
20
30
40
50
[emim]OAc [DBNH]OAc [TMGH]OAc NMMO
bire
fring
ence
DR
103
[emim][OAc] fibers: orientation develops poorly due to lowresilience in the core.
[TMGH][OAc] fibers: solidified gel->solution behaves as a permanent network.
Fiber orientation vs. DR
L. K. J. Hauru, M. Hummel, K. Nieminen, A. Michud and H. Sixta. Soft Matter, 2016, 12, 1487--1495
L. K. J. Hauru, M. Hummel, K. Nieminen, A. Michud and H. Sixta. Soft Matter, 2016, 12, 1487--1495
Yield strain and stress decrease at 0.5 nH2O/nIL obviouslydue to a low water diffusion.Telescopic-type breach because of very low resilience in the core during the onset of regeneration.
Incipient [emim][OAc] filament
Michud et al. Polymer 75 (2015), 1-9
0 5 10 1510
20
30
40
50
60
Tena
city
(cN
/tex)
Draw ratio
Blend 1 - 15% Blend 2 - 15% Blend 4 - 13% Blend 5 - 15% Blend 6 - 13% Blend 6 - 15%
Molecular Weight of the Solute
0 1 2 3
2x103
4x103
6x103
8x103
G',
G'' a
t CO
P (P
a)
Angular frequency of COP (s-1)
Blend 1 - 15% Blend 2 - 15% Blend 3 - 15% / Blend 4 - 13/15% Blend 5 - 15% / Blend 6 - 13/15% / Euca. - 13/15%
103 104 105 106 107
Molar Mass (Da)
Blend 2PDI 5.9
6.9 23.9
103 104 105 106 107
Molar Mass (Da)
Blend 1PDI 5.3
6.8 12.5
103 104 105 106 107
Molar Mass (Da)
Blend 3PDI 2.1
1.0 19.6
103 104 105 106 107
Molar Mass (Da)
Blend 6PDI 3.4
3.5 22.5
PART 4
Fiber properties• First generation ILs• Acid-superbase conjugates• Structure-property relationship
IL-spinning in literature
[amim
]Cl
[bmim]C
l[em
im]O
Ac[bmim
]OAc
[emim
]dep0
20
40
60
Tena
city
cond
(cN
/tex)
Lenz. Ber (2005), 84:71-85Lenz. Ber (2006), 86:154-161Lenz. Ber (2006), 86:144-153Cellulose (2005), 85:59-66Macromol Mater Eng (2010), 295:676-681Polym Eng Sci (2012), 52:1708-1714
J Appl Polym Sci (2010), 115:1047-1053J Appl Polym Sci (2013), 128:4141-4150Cellulose (2012), 19:1075-1083Patent DE102012005489A1ACS Sustainable Chem&Eng (2016), 4:4545-4553Patent WO2013/144082A2
• Reaction of imidazolium cationwith the REG
• Formation of carboxylic acids, HCOOH, as a result of pulpdegradation
Ebner, G. et al. Tetrahedron Letters (2008), 49(51), 7322)
• High temperature > 100°C
• Poor spinnability
• Corrosion
• Excessive DP degradation
Successfully spun fibers fromAcid-Superbase Conjugates cellulose solutions
0 5 10 1520
30
40
50
60
Tena
city
(cN
/tex)
Draw ratio
13 wt% [DBNH][OAc] 13 wt% NMMO
Birch PHK
3 4 5 6 70,0
0,2
0,4
0,6
0,8
Diff
eren
tial M
ass
Frac
tion
Log Molar Mass
Birch PHK (312/69) NMMO (298/70) [DBNH][OAc] (328/76)
Substrates Cell%
Titerdtex
TenacitycN/tex
Elong%
NMMO-fibre 13 1.53 54.3 11.2
[DBNH][OAc] fibre 13 1.55 58.5 11.0
Unpublished results
Opportunities: Strong fibers with uniform nanostructure
30% Lignin, DR=10.6Ftot = 0.456
Pure cellulose, DR=10.6Ftot = 0.685
Asaadi, S.; Nishiyama, Y.; Sixta, H. unpublished results Hailwood, A.J. and S. Horrobin, Trans. Faraday Soc., 1946. 42B: p. 84-92, discussion 94-102
0 5 10 15 20 250
200
400
600
800
1000
CuproViscose, CV
NMMO
Tena
city
cond
[MP
a]
Elongationcond [%]
IONCELL
Modal, CMD
0 5 10 150,4
0,5
0,6
0,7
0,8
0,9
1,0f(c), f(a)
Draw ratio [ ]
f(c)
f(a)
Sixta, H. et al. NPPRJ, 30(1), 2015, 43-57
PART 5
Solvent Recycling• Removal of Water• Challenge of limited ionicity of
protic acidic ionic liquids
Premixing Dissolution SpinningFiltration
Washing, cutting, pre-conditioning,
drying
Pulp
Staplefibers
Evaporation
Water
Water
Water
c(IL) < 20 wt%
EvaporationPurification
Purification
IL preparationImpurities
MakeupIionic liquid
Water
A C
Water
Water
c(IL) < 20 wt%
Challenge: Solvent recycling
Thin film evaporator (RF10, UIC GmbH)
Ostonen, A. (2017). Doctoral Thesis, Aalto 9/2017.Hauru, L.. Et al. (2016). Soft Matter, 12, 1487-1495Pariainen, A. et al. ChemSusChem, 2013, 6, 2161-2169
Strong interaction between IL& water‒ Tolerable water content < 8 wt%‒ Achieved water content < 3 wt%
Removal of water
Acc. Chem. Res. 2007, 40(11), 1228-1236JACS (2003), 125-15411-15419
Hydrolytic instability of of DBN
• Vaporized DBN hydrolyses very fast to APP• in the condensate APPAc formed only at drastic conditions. • DBN regeneration by acid catalysis (reversion)
23
PART 6
Conclusions
• Acid-superbase conjugate ionic liquids currentlythe only promising class of ILs capable for theproduction of strong man-made cellulose fibres.
• However, solvent recovery challenging due to losses of small neutral base fractions.
• Opportunities exist to achieve the requested almostquantitative solvent recycling rate.
Acknowledgement