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Herbert Sixta, June 2016
Postgraduate course on
Cellulose ChemistryIntroduction
Aim of the Course
• Comprehensive overview of the fundamentals in cellulose chemistry and physics.
• Sources of pure cellulose, cellulose functionalization, new cellulose solvents…
• Representative survey of the current and future cellulose industry.
• Cellulose structure and morphology
• Cellulose-based products
Lecturers (12)
Guest lecturers- Yoshi Nishiyama, Professor, Cermav, Grenoble France.- Haio Harms, former CEO Kelheim, Germany- Tekla Tammelin, Docent, VTT, Espoo, Finland.- Alistair King, Docent, University of Helsinki, Helsinki, Finland
Aalto University, School of Chemical Technology- Tatiana Budtova, Professor, Aalto and Cemef, Sophia-Antipolis- Mark Hughes, Professor- Michael Hummel, Staff Scientist- Eero Kontturi, Professor- Thad Maloney, Professor- Maija-Liisa Mattinen, Docent- Ilari Filpponen, Docent- Herbert Sixta, Professor
Literature, Course Material
1. Pdf files of all lecture notes and literature recommendations.
2. Cellulose Science and Technology: J-L Wertz, O. Bedueand J.P. Mercier. EPFL Press, 2010.
3. Cellulose: Structure, Accessibility and Reactivity Hans A. Krässig. Polymer Monographs, Vol 11. Gordon and Breach Publishers, 1993.
4. The Structures of Cellulose: R.H. Atalla. ACS Symposium Series 340, 1987
Literature, Course Material
5. Cellulose Solvents. T.F. Liebert, T.J. Heinze, K.J. Edgar, ACS Symposium Series 1030, 2009
6. Regenerated Cellulose Fibers: Calvin Woodings. WoodheadPublishing Limited, 2001.
7. Cellulose Acetates: Properties and Applications. P. Rustemeyer. Macromolecular Symposia, Wiley-VCH, 2004.
8. Comprehensive Cellulose Chemistry. D. Klemm et al., Wiley-VCH, 1998.
9. Crystalline Cellulose and Cellulose Derivatives: P. Zugenmaier, Springer 2008, ISBN 978-3-540-73933-3
Literature, Course Material
10. Physical proeprties of textile fibers, 4th Edition. W.E. Morton and J.W.S. Hearle, The Textile Institute (2008)
11. Handbook of Fiber Chemistry, 3rd Edition. Menachem Lewin, CRC Press, International Science and Technology Series (2005).
12. Cellulose Fibers: Bio- and Nanopolymer Composites. Green Chemistry and Technology. Springer, Susheel Kalia, B.S. Kaith, Inderjeet Kaur (2011).
13. Bacterial NanoCellulose. Miguel Gama, Paul Gatenolm, Dieter Klemm. CRC Press, Perspectives in Nanotechnology (2013).
14. Nanocellulose. From nature to high performance tailored materials. Alain Dufresne, De Gruyter (2012)
Coordination of PaPSaT Course
• Course leader: Herbert Sixta, [email protected], +358 50 384 1764
• Course arrangements: Coordinator Leena Hauhio, [email protected]
Course Evaluation
• 8 ECTS• 30 h Lectures• Scientific Review Report written as a
scientific review article ~ 25 pages
Topics for the Scientific Review Article
1. Dissolving pulps for cellulose chemical processing.2. X-ray and NMR-methods for cellulose structural
characterization.3. Supramolecular structure of cellulose.4. Morphological structure of cellulose.5. Methods of cellulose activation.6. (Direct) Cellulose solvents7. Enzymatic hydrolysis versus chemical degradation of
cellulose.8. Oxidative degradation of cellulose.9. Thermal degradation of cellulose.
Topics for Scientific Report
10.Mechanical and radiation degradation of cellulose.11.Esterification of cellulose.12.Cellulose acetates: properties and applications.13.Crosslinking of cellulose.14.Grafting of cellulose.15.Actual overview on regenerated cellulose fibers.16.Novel cellulose products.
Topics for Scientific Report
17.New ways of degrading cellulose with heterogeneous catalysts: hydrogenation reactions and solid acid catalysts.
18.The use of nanofibrillar cellulose in composite materials.
19.Liquid crystal properties of cellulose nanocrystal suspensions.
20.Novel homogeneous cellulose derivatization routes.
Topics for Scientific Report
21.Fundamentals of Cellulose ether production:– Possible ether forming reactions– Pathways to regioselective functionalized cellulose ethers.– Basic reactions of industrial etherification
22. Industrial production of cellulose ethers– Principles of industrial production processes– Main side reactions– Cellulose ethers with commercial importance– Main applications of cellulose ethers
Topics for Scientific Report
23.Physical properties of Cellulose ethers:– Thermogelation of methyl hydroxyalkyl cellulose ethers– Rheology of aqueous solutions of cellulose ethers.
24. Others: you can choose own topics provided that they are related to cellulose
Time Schedule
Submission deadline of the scientific reviewarticle is Nov 30st
(no prolongation possible)
Historic review
1845
Ch-F SchöbeinCellulose nitrate
dissolved in etherand alcohol
1855
G-P Audemars:First fibres produced;
no practical applications
1883
J-W SwanFirst commecialfibers; precip in
EtOH
1889
Hilaire de ChardonnetYarns and fabrics shown at the world exhibition in Paris
1890
Besancon50 kg/d productionfounder of chemical
fiber industry
18911900-1910 >1910
Start-ups in many
countries
Cellulose nitrateDopetank
Cellulose nitrated withnitric and sulfuric acids,dissolved in alcohol ether
Washing, waterdenitration Denitration((NH4)2S)& stretching of cellulose
nitrate filaments
Not competitive: closures, conversions
into viscose
Evaporation of ethanoland ether
Lastclosuresafter1935
FILTERTOW
Production sites: US, UK, France, Belgium, Germany, Switzerland
MilesCellulose diacetate (CDA),
soluble in acetone: coatingsfor airplanes
1865
SchutzenbergerCellulose acetatesynthesized with
A.A
1879
FranchimontIntroduced sulfuric acid
as catalyst
1903
EichengrunSoluble CTA for
casting films
1904
Camille and Henri DREYFUS
Laqueur, films.
19141917
1927
DREYFUSFirst CDA plant
in US
Cellulose acetate
DREYFUSFirst CDA plants in
France, Italy, England
Paul Schȕtzenberger1829 - 1897
Dry Spinning
Arthur Eichengrȕn1867-1949
AfterWW II 1952
Production sites in Japan (Daicel,
Mitsubishi) and Korea (Sunkyong).
Brief History of Textiles
1. 36.000 BC flax fibers were found in the Republic of Georgia. 2. Since the Neolithicum, the use of natural fibers, as we use them still today, wool,
linen, silk, hemp, abaca, cotton and leather, to name a few, have been used for textiles and clothing.
Industrial Production of Textiles
1857
M.E. Schweizer: Cellulose dissolvesin Cu(OH)2 / NH3
1890
L-H. Despaissis: FP203 741; technical
application
1899
Fremery&Urban(Elberfeld):
first textile fibres
1901
J.P. Bemberg AG (Wuppertal)
E. Thiele stretch-spinning (Linters): Bemberg™ silk
1931
Asahi KaseiStarted operationsin Nobeoka/Japan
1980s
Stop of Cuprofiber production(Bemberg™) in
Germany
2000 2015
Asahi KaseiOnly producer,
15.000 t/a
Asahi Kaseiexpanded the
capacity to 17.000 t/a
Cuprammonium Process ”Cupro”
Dopetank
Cellulose (Linters) in[Cu(NH3)4(H2O)](OH)2
water H2SO4
Skin care
Wipers
Lining
Outerwear
Innerwear
Home textiles
1885
AlkalicelluloseCh-F Cross
1892
GB 8700C.F. Cross, E.J.
Bevan, C. Beadle
1899 1905
Courtauldspurchased patents &
started viscoseproduction in Coventry
19311943
Polynosic(Toramomen)
19501955-1965
High wet-modulus (HWM)
Modifiers+Zn(II)
Reducingenvironm impact:
CS2+H2SRecycling; wastewater treatment
Viscose process
Stretch bath
Stretch unit
Spinningpump Spin bath
take-up godet
Spinningpipe
spinneret
overflowFiltercartridge
Spin bathregeneration
Exhaust
Viscose Spinning Syndicate(near London; Cross and Stearn) Topham developed the first Pt-
spinnerets
Lilienfeld64% H2SO4 as
spin bath; Ten~60 cN/tex
Modifier (Cox) Super tire
yarn40 cN/tex
1965-1985
Regular Viscose& Modal process
optim.: stronger, moredurable
1985-1995
Speciality fibers
ImprovedDissolving pulps
1995-2015
Apparel, bedlinen, upholstery, carpets, technical textiles, wipes, paper,
1939
GraenacherUS 2,179,181;
tertiary amine oxideas cellulose solvent
D.L. JohnsonUS 3,447,939
Kodak; NMMO as cellulose solvent
1969 19691979
19791982
Lenzing AGStarted research
On Lyocell
1989 1992
Mobile, USAFirst commecial
plant of Courtauld
Grimsby, UKSecond commercialplant of Courtauld
Lyocell process
American Enca/Akzona Inc.Developed the basics of the
spinning process; decided not to scale up
Courtauldstarted research
on Lyocell:Tencel®
BISFANew generic
name - Lyocell
1997
HeiligenkreuzFirst commecialplant of Lenzing
AG
1998 2005
Apparel, bedlinen, upholstery, carpets, technical textiles, wipes, paper,
2014
LenzingForth commercialTencel plant (67
kt)
Lenzing AGacquires Tencel group(Grimsby+Mobile) on
5/05/2005
2015
222 ktAnnual Tencel
capacity
Market, technologyoverview
Sources: IHS, ICAC, CIRFS, Fiber Economics Bureau, National Statistics, The Fiber Year 2015;
Drivers for the Textile Fibers
1970 1980 1990 2000 2010 20200
20
40
60
80
100 Million tonnes
population (billion)
3
6
9
12
15
18
1970 1980 1990 2000 2010 20200
20
40
60
80
100
kg per capita
population (billion)
3
6
9
12
15
18
1970 1980 1990 2000 2010 20200
20
40
60
80
100
kg per capita
Million tonnes
population (billion)
3
6
9
12
15
18
Cellulose man-made fiber market
1940 1960 1980 20000
2
4
6Cellulosic Fiber ProductionMillion tonnes
Staple fiber Filament
1990 2000 2010 20200
200
3000
6000
9000 kt/a
Years
Tenc
el
Viscose and other Cellulosics
The Fiber Year 2016
Commercial CelluloseProducts
Nitrocellulose0.15 Mio t/a
Cellulose Ether0.50 Mio t/a
Spec. Paper0.14 Mio t/a
MCC0.18 Mio t/a
Acetate Fibres0.60 Mio t/a
Acetate Film0.30 Mio t/a
Lyocell Fibres0.23 Mio t/a
Film, Casings0.15 Mio t/a
Viscose Fibres4.5 Mio t/a
23 – 28 Mio t/aCOTTON
Regenerated CelluloseProducts
OO
OO
OO
O O
O
HH
H
H
O H
OH
n
ViscoseCS2/NaOH
CarbamateNaOH/urea in o-
xylene *
BioCelsolEnzyme/NaOH/ZnO
(urea/thiourea)
MichelinFormate/air
gap/saponified
DuPontAcetate in
TFA/HCOOH/steamdrawn/saponified
FortisanAcetate/acetone spun, saponified
Cupro[Cu(NH3)4](OH)2
LYOCELL (a) NMMO.MH(b) Ionic liquids
*CarbaCell®
WATERSupercriticalconditions
FILMSMembranes, Battery separator
HYDROGELS
NONWOVENSWipes, Meltblown
TEXTILESApparel, Accessories
HOMETEXCOMPOSITESAEROGELS
POWDER
SPONGES
CARBON FIBERS
CLY
Aerocell
Cellulose Solution Shaping Wet gel
CelluloseAerogel
CarbonAerogel
NMMONon-solvent Solvent
exchange
Supercritical drying
pyrolysis
Shrinkage upon drying
EU Project Aerocell, 50588-1, 01/2004-31/12/2006: Lenzing AG, Ecole des Mines de Paris, Cognis, Fraunhofer IAP, Genialab, LEMPI Grenoble.
Aerocell
NMMO, pulp Shaping Cellulose hydrogel
Supercriticaldrying
CelluloseAerogels
BET surface area: 50 – 400 (250) m2g-1
Density: 0.02 – 0.10 (0.06) gcm-3
EU Project Aerocell, 50588-1, 01/2004-31/12/2006: Lenzing AG, Ecole des Mines de Paris, Cognis, Fraunhofer IAP, Genialab, LEMPI Grenoble.
beads
Hydrogel – Wound Care
− Water content 98.4%− BET = 150 m2g-1
− Two routes: (a) partly dissolved, ”frozen dope” (b) dissolved, ”molted dope”
J. Innerlohinger et al. (2006)
MicroGel for Films and Coatings
- Transparent films- Coatings- Food additive- Rheology modifier- Binder for active substances- Drug delivery system- Implants replacing silicones- Artifical heart valves
(Dilute)CelluloseSolution
Precipitation
Wetmilling
NMMO
pulpHighly viscousShear-thinning
GEL
J. Innerlohinger et al. WO 2013/006876 A1Opietnik, M. et al. Lenz. Ber (2013), Vol 91, 89.92
wateradditives
Non-fibrous
Lyocell GEL Pulp GEL
Tencel® gel coatings
Hydrophobic Fiber
• Treated with aqueous solution of alkylketene dimers
• Surface energy 35 mN/m (water has 73)• Floats on water• Very soft• Oil absorbent Lyocell fiber• Wipes application
Schachtner, B. Maier A. Lenz. Ber. (2013), Vol 91, 52-55WO 2013/067556 A1
Spheric Cellulose Powder
- Filter aid- Food additive- Tableting aid- Cosmetics- Chromatography- …
CelluloseSolution
Supercoolsolidific Grinding
NMMO
water
pulpRegener.Washing
Drying
PS = 10 – 200 m
J. Innerlohinger et al. PCT 2009/036480 A1
Cellulose Meltblown Nonwovens
One-step Nonwovens production:Cellulose solution ejected through a mulitplicity of small orificies into air and the filaments are picked up by a turbulent gas stream and converted to a fleece.
M. Luo et al. PCT 98/07911
H. Ebeling et al. Lenz. Ber. 86, 124-131 (2006)
Running meltblown plant in Golm, IAP, Fraunhofer
Meltblown fibre fleece
Precursor Fibers for Carbon Fibers
zone 1
zone 2
zone 3
zone 4
whitefiber
blackfiber
Oxidation/stabilization
LT furnace HT furnace
Carbonization Graphitization
Precursor Fibers
Submitted to Journal of Material Chemistry A
Carbon fibers40% Lignin60% Cellulose
E > 70 GPaT > 1.4 GPa
Winding on the bobbin
Cellulose Acetates
Solubility shifts to more non-polar solvents with increasing DS. Deactylation rate down to DS 2.2 comparable-> even DS distribution.
O
OH
OHOOH
O
O
O
CH3COOH
O
O
OOO
O
O
O
catalyste.g. H2SO4
H2OH+
CTA(dichloromethane)
CDA(acetone)DS 2.0-2.6
Thomas Heinze, Tim Liebert. Macromol. Symp. 208, 167-237, 2004
Cellulose Acetates Applications
P. Rustemeyer(editor). Macromol. Symp. 208, 2004
CDA CTA
Membranefiltration(1.8-2.8)Hemodial.,Desalin, Lab filtr., WaterpurificationAcetate solution in acetone+salt is castedat low temp-> evapacetone
BeadsChromat sep., (enantiomer1) cosmetics, leucocyt ads2.,Acetate solutionin CH2Cl2 +non-solvent
*Daicel Chemical, e.g. Chiralcel O®2Adacolumn® 3Fuji Photo Fil Co.Ltd, Daicel, 4Clarifoil® (Celanese)
CellulosePlastic(2.2-2.5)Diacetatepowder+plastic-> mixing->extrusion: Injected-mouldedarticles
CTA FilmPhotographicfilm, Optical compensationfilm for LCD3
CDA Film4
(2.5) Print lamin., food packag., adhes. tape Acetone sol. + plast->casting, drying
TextileApplicationLining, medicalgauze, ribbons,..
CA Filter Tow(2.5) Cigarette filtermade from crimpedendless CA filaments
Cellulose Derivatives
1. Cellulose esters
2. Cellulose ethers
Cellulose Acetate
DS Solvent Application
1.8 - 1.9 water/prop-OH-CHCl3 fabric
2.2 - 2.3 acetone lacquer, plastic
2.3 - 2.4 acetone rayon fibre
2.5 - 2.6 acetone film
2.8 - 2.9 dichloromethane insulating sheet
2.9 - 3.0 dichloromethane textiles
Solubility shifts to more non-polar solvents with increasing DS. Deactylation rate down to DS 2.2 comparable-> even DS distribution.
Thomas Heinze, Tim Liebert. Macromol. Symp. 208, 167-237, 2004
Acetylation of Cellulose
43
Cellulose Acetates Applications
P. Rustemeyer(editor). Macromol. Symp. 208, 2004
CDA CTA
Membranefiltration(1.8-2.8)Hemodial.,Desalin, Lab filtr., WaterpurificationAcetate solution in acetone+salt is castedat low temp-> evapacetone
BeadsChromat sep., (enantiomer1) cosmetics, leucocyt ads2.,Acetate solutionin CH2Cl2 +non-solvent
*Daicel Chemical, e.g. Chiralcel O®2Adacolumn® 3Fuji Photo Fil Co.Ltd, Daicel, 4Clarifoil® (Celanese)
CellulosePlastic(2.2-2.5)Diacetatepowder+plastic-> mixing->extrusion: Injected-mouldedarticles
CTA FilmPhotographicfilm, Optical compensationfilm for LCD3
CDA Film4
(2.5) Print lamin., food packag., adhes. tape Acetone sol. + plast->casting, drying
TextileApplicationLining, medicalgauze, ribbons,..
CA Filter Tow(2.5) Cigarette filtermade from crimped endless CA filaments
Stein, Rhodia 2011
Spinning (Filter Tow)
Applications
• Thermoplastics– Granules for screwdriver handles, brushes, injected-moulded articles for
costume jewellery and hair ornaments, sheets for eyeglasses and safety goggles
– Fims for packaging, adhesive tape and magic tape, shoelaces, sequins– Sheets for eyewear, costume jewellery, hair ornaments (handcrafted);
athletic and safety visors, casino chips, buttons, handbags and handles
• Biocomposites
• Liquid Crystal Display
Stein, Rhodia 2011
Thermoplastics
A. Stein, 2011
Granule
PlasticizerDiacetate Powder
Mixingblending Additives and colorants,
maturation
Process flowchart
Biocomposites from CA
47A. Stein, 2011
Cellulose Nitrate
DS Solvent Application1.9 - 2.0 ethanol plastic1.9 - 2.3 ester, ethanol lacquer2.0 - 2.3 Ester film2.4 - 2.8 Aceton explosive
2 ⇌ 2
⇌ ⇌
49
Nitrocellulose
OO O
O
ONO2
OHO2NO
ONO2
ONO2
HO OO O
O
ONO2
ONO2HO
ONO2
ONO2
HO
Nitrocellulose
50
Lacquer and brilliant paints
Wood, metal, paper lacquer, nail polish, printing ink
Nitrocellulose Application
Cellulose Derivatives
1. Cellulose esters
2. Cellulose ethers
History
• 1912 First patents on alkyl-, carboxymethyl, benzyl- and hydroxyethyl cellulose
• 1920 First industrial production in in Germany: Carboxymethylcellulose (CMC)
• 1927 First technical production of methylcellulosewith methylchloride based on a patent of Sponsel (1925).
52
Basic reactions of industrial etherification
53
O
OO
OO O
HOOH
OH
HOO
OH
O
HO
O
O
O
OCH3
H3COOCH3
OO
OHO
O
CH3
HO
O
O-
Na+
Multifunctionality of Cellulose
Commercial Ethers
• Cellulose ether, anionic CMC, CMHEC (360 kt/a)
• Cellulose ether, neutral EC, MC, HEMC, HPMC, HEC, HPC, EHEC (300 kt/a)
• Cellulose ether, cationic Polyquaternium-10 (quaternery ammonium compound; applications in cosmetics) (30 kt/a)
55
Reactivity of OH groups
With increasingalkali amount the substitution on the primary hydroxygroups is preferred
56
0,0 0,5 1,0 1,50
3
6
9
C-2
C-3
Rea
ctiv
ity o
f OH
gro
up
mol NaOH / mol AHG
C-6
R. Dönges, Das Papier 1997, 12, 653-660
OO
OOO
O HH
H
23
6
Dow Wolff Cellulosics (Germany, Belgium, US): 85 kt MC, 35 kt HEC
Shin Etsu: (Germany, Japan): 63 kt MC, 10 kt HEC
Hercules / Aqualon (US, Belgium, China, Netherlands): 44 kt MC, 52 kt HEC
Akzo Nobel (Sweden) 26 kt HEC
Samsung Chemicals (South Korea): 15 kt MC
Major players on CE market in 2007
Source: SRI Consulting
58
GelificationFood additive
Shear thinningOil production
Thickeningcosmetics
SizingPaper production
O
O- Na +O
O- Na +
OO
OO
O
OHHO
O
OHHO O
OO
O
O
OHHO
O
OHHO
O- Na +
O O- Na +
O
CMC - Final Product Applications