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, herbert.sixta@aalto.fi, +358 50 384 1764

• Course arrangements: Coordinator Leena Hauhio, leena.hauhio@aalto.fi

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