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) (

) (

1963

X R D

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) (

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P roperties of natural & s ynthetic fibers

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2008

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C ellulos e

3 0

Reaction of the OH group: esters, ethers, etc.

DS=degree of substitution is important: DS=0-3/glucose
The DS is dependent on the availability of OH groups so it is a function of
the H-bonding in cellulose!

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R eaction of C ellulos e Acetate

Esters commercially made by Eastman.
Mostly short fibers for non-wovens like cigarette butts!

-C

= -

Relies on acetylated OH groups

ester linkages!

Opartial

cellulose + acetic acid + acetic anhydride + H2SO4

hydrolysis

dissolve in acetone and spin fiber

Cellulose will react under anhydrous conditions in the presence of acid catalyst
and acetic anhydride to form cellulose tri-acetate. Cellulose acetate is the partially
acetylated product of high purity cellulose and acetic anhydride. It is obtained by
acid catalyzed hydrolysis of the tri-acetate to a DSav ~2.4
(cellulose tri-acetate would be DS~3.0)

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2.4

C ellulos e Acetate

OH
CH3

+H
CH3

OH
OCOCH3

CH3

O
+ Cell

C
HO

OCOCH3

OCOCH3
Cell

O
CH3

OCOCH3
O
CH3

Cell

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D S of C ellulose Acetate
C-OH + (CH3CO) 2O
OH group on
cellulose

acetic anhydride

C-OOCCH 3
H2SO4
(sulfuric acid)

cellulose triacetate=ester

CH3COOH
acetic acid (H from
cellulose OH)

0.2
0.8

acetic anhydride is split in 1/2

C-OOCCH 3 + 0.2H2O
hydrolysis

this is fully acetylated cellulose

cellulose triacetate=ester

C-(OOCCH3)0.8
(OH)0.2

+ 0.2CH3COOH
acetic acid

cellulose acetate=ester

DS=3(0.8)=2.4/glucose can be v. high!

3

2.4

This material is soluble in acetone and other organic solvents

Properties, like biodegradability, are f(DS): remember, the biggest
impediment to this rxn is the availability of OHs from H-bonding

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D egree of polymerization

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His tory of C ellulos e ac etate

(zyl, z ylonite, C ellon and R hodoid)

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Paul Schtzenberger discovered cellulose acetate in 1865

George Miles more solvents in 1904
Camille and Henri Dreyfus in 1910
DOPE
In1914,The British Cellulose and Chemical Manufacturing Co - 1918 to
British Celanese Ltd
In 1918 The American Cellulose & Chemical Manufacturing Company in
New York by the Dreyfus brothers In 1927- the Celanese Corporation of
America
Mazzucchelli ,Celluloid Acetate sheets and Cellulose Nitrate
Cellulose acetate film was introduced in 1934
IBM in 1952 for use on their IBM 726 tape drive in the IBM 701 computer

F iber properties

H and: s oft, smooth, dry, cris p, resilient

C omfort: breathes , wicks , dries quickly, no static cling
D rape: linings move with the body linings conform to the garment
C olor: deep brilliant s hades with atmos pheric dyeing meet colorfas tness
requirements
L us ter: light reflection creates a signature appearance
P erformance: colorfas t to pers piration s taining, colorfas t to dry cleaning, air
and vapor permeable
Tenacity: weak fiber with breaking tenacity of 1.2 to 1.4 g/d; rapidly los es
s trength when wet; mus t be dry cleaned
A bras ion: poor res is tance
H eat retention: poor thermal retention; no allergenic potential
(hypoallergenic)
D yeability: (two methods ) cross -dying method where yarns of one fiber and
thos e of another fiber are woven into a fabric in a desired pattern; s olutiondying method provides excellent color fas tness under the effects of s unlight,
pers piration, air contaminants and was hing

.....

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P roduction method
P urified c ellulos e from wood pulp or c otton linters .
Mixed with g lac ial ac etic ac id, ac etic anhydride, and a
catalys t
Ag ed 20 hours - partial hydrolys is occ urs
P recipitated as ac id-res in flakes
F lakes dis s olved in ac etone
S olution is filtered
S pinning s olution extruded in c olumn of warm air.
S olvent rec overed
F ilaments are s tretched and wound onto beams , c ones ,
or bobbins ready for us e

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Acetate fiber characteris tics

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cellulos ic a nd thermoplas tic

s elective abs orption a nd remova l of low levels of certain orga nic c hemica ls
eas ily bo nded with plas ticiz ers , heat, a nd pres s ure
aceta te is s oluble in ma ny commo n s o lvents (es pecia lly ac eto ne a nd other org a nic
s olvents ) a nd c a n be modified to be s oluble in a lternative s olve nts , inc luding wa ter
hydrophilic: acetate wets eas ily, with good liquid tra ns port a nd exc ellent abs orption; in
textile applica tions , it provides comfort a nd a bs orbency, but a ls o los es s trength when
wet
aceta te fibers a re hypoallerg enic
hig h s urface area
made from a renewable res ource: wood pulp
ca n be compos ted or incinera ted
ca n be dyed, however s pecia l dyes a nd pigments are required s inc e acetate does not
accept dyes ordina rily us ed for cotton a nd rayon (this a ls o a llo ws c ros s -dyeing )
res is ta nt to mold a nd mildew
eas ily wea kened by s trong a lkaline s olutio ns a nd s tro ng o xidiz ing ag ents .
ca n us ua lly be wa s hed or dry c lea ned; g enera lly does not s hrink

Vis c oelas tic B ehavior of

C ellulos e Ac etate

Cellulose acetate (CA)/N,N-dimethylacetamide (DMA)/water

phase-separated gel formation
beta (1-4)-linked anhydroglucopyranose units(AGU)
substituted at the C-2, 3-, and 6-positions of the AGU
DS 0.5-1 soluble in aqueous solutions
(DMA) dissolves CA of DS ranging from 0.49 to 2.92
Solvent evaporation, changes in temperature, or the addition of a
nonsolvent
sol-gel transition
Hansen hydrogen-bonding solubility parameter index
Confocal scanning laser microscopy (CSLM)

...........

1 0.5


2.92 0.49


CSLM

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Mixed cellulos e es ters (MC E )

C ellulos e acetate-propionate (C A P )
C ellulos e acetate-butyrate (C A B )

Cellulose acetate-phtalates

mixed acetic-aliphatic cellulose esters

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butyric or hexanoic anhydrides or maleic anhydride

thermoplastic applications

coating applications

high hydrophobicity

Water contact angles

Water contact angles

Water vapor s orption

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http://en.wikipedia.org/wiki/Cellulose_acetate
http://en.wikipedia.org/wiki/Cellulose
http://chemistry.about.com/od/factsstructures/ig/ChemicalStructures/CelluloseAcetate.htm
http://www.qrbiz.com/buy_cellulose-acetate-pellets
http://chemical.ihs.com/nl/Public/2009/0908/0908.html
http://renewablemat.bse.vt.edu/teaching/BSE%204514/Lecture%203%20
http://staffweb.itsligo.ie/staff/mabroaders/webbased/Envsci/ES4/WM%
http://www.ri.cmu.edu/pub_files/pub4/lopez_george_2004_1/lopez_george_2004_1.pdf
http://www.che.ncsu.edu/khangroup/Papers/Appaw_Biomacromolecules_2007.pdf
Callum A.S. Hill, Wood Modification: Chemical, Thermal and Other Processes
Collins Appaw,Richard D. Gilbert,Saad A. Khan, Viscoelastic Behavior of Cellulose Acetate
in a Mixed Solvent system
Jrme Peydecastaing, Chemical modification of wood by mixed anhydrides
Minna Blomstedt,MODIFICATION OF CELLULOSIC FIBERS BY CARBOXYMETHYL
CELLULOSE
Monica Ek,Gran Gellerstedt,Gunnar Henriksson,Pulp and Paper Chemistry & Technology
Paul Gatenholm,Hemicelluloses:Science and Technology
Peter Zugenmaier, Crystalline Cellulose and Derivatives, 2008 Springer