Fibic thermoplastic cellulose final public seminar 15 4 2014

1
Finnish Bioeconomy Cluster FIBIC Oy
FuBio Cellulose- WP3
WP 3 - New products
Thermoplastic cellulose derivatives
Fubio Cellulose Seminar 14.4.2014
Sauli Vuoti, Jaakko Hiltunen, Riku Talja, Lisa Wikström
Pia Willberg-Keyriläinen
Sauli.Vuoti@vtt.fi

2
THERMOPLASTICITY – DEFINITION AND USES
• Thermoplastic is a polymer that turns to a liquid when heated and freezes to a rigid
state when cooled sufficiently. The melting – freezing process can be repeated. In
the case of polysaccharide-based materials, the term “thermomeltable” is often
used.
• Thermoplastic materials can be processed by melt processing e.g. by using extrusion
(films, fibres) or injection moulding
– A wide range of thermoplastic polymers are commercially available:
polypropylene, polyethylene, polylactide etc.
– Known cellulose-based commercial thermoplastics are cellulose acetates (CA) or
cellulose mixed esters, such as cellulose acetate butyrate (CAB)
• Some thermoplastics are amorphous polymers
– as the temperature increases, the amorphous polymer will soften
gradually
– the defining temperature for amorphous polymers is the glass
transition temperature (Tg). Below this temperature, the
amorphous chains become immobilized and rigid and behave
like glass.Finnish Bioeconomy Cluster FIBIC Oy

3
• Thermoplastic cellulose acetates and mixed esters (CA, CAB) have mainly been used
for production of sporting goods, eyeglass frames, cosmetic packaging, coatings,
films, toys etc. but in smaller volumes
• The limiting factor for their use has been the price of the materials
• Processing of cellulose has demanded two-step processes that include either the
regeneration or homogenization of cellulose prior to reaction, or derivatization of
cellulose to acquire the necessary solubility followed by a second chemical
modification and in some cases also de-acetylation
THERMOPLASTICITY – DEFINITION AND USES
• Academic solutions also exist: (homogeneous)
hydroxypropylation or methylation followed by
acetylation or esterification (acid chlorides) or
silylcarbamates  non-industrial price
• In all cases cellulose content of the materials is
< 50%

4
APPROACH IN THIS PROJECT
Transparent cellulose film
High-
consistency
reaction
Mixed
cellulose
esterHeat-pressing
ECONOMIC AIMS
o Cellulose content >
50%
o No solvents needed
o High-consistency
processing
o Single-step
reactions /
Heterogeneous
processes
o No need for
pretreatments
(Domsjö)
o High acetyl content
+ small quantity of
fatty acid

5
COMMERCIAL BOUNDARIES
Cellulose content in cellulose acetate laurate
30,0 %
40,0 %
50,0 %
60,0 %
70,0 %
80,0 %
90,0 %
0 0,5 1 1,5 2 2,5 3
wt%ofcellulose
Acetyl DS
Lauryl DS 0.2
Lauryl DS 0.3
Lauryl DS 0.5
Lauryl DS 0.7
Lauryl DS 0.9
Likely not thermomeltable
Likely thermomeltable but
low cellulose content
Possible
operating
window
Juha Leppävuori, Eemeli Hytönen et al.

6
Cellulose Reagent Reagents
(eq)
Received
DS
Domsjö
(mech.
treatment)
Acetic
anhydride
Lauric acid
4
1.6
2
0.2
Domsjö
(enz.
treatment)
Acetic
anhydride
Lauric acid
4
1.6
2.0
0.2
Domsjö
(mech.
treatment)
Acetic
anhydride
Lauric acid
3
4
1.5
0.5
CHEMICAL MODIFICATIONS
- Close to one hundred derivatives
were prepared during this project
according to known literature
methods
- Main derivatives were hexanoates
and laurates or mixed esters
(acetate hexanoate or acetate
laurate)
- Hexanoates and laurates were
thermomeltable but poorly
soluble, but Tg and degradation
temperature close to each other
- Mixed esters were thermomeltable
and soluble up to a certain content
of the fatty acid
- Purification was difficult and
thermomeltability cannot always
be confirmed

7
Cellulose
C1Carbonyl
-CH3
acetate
-CH3
laurate
13C NMR spectrum of the cellulose mixed ester (acetate-laurate ester) in CDCl3
(DSacet= 2.4, DSlaur= 0.2)
13C-NMR SPECTRUM OF CELLULOSE
ACETATE LAURATE
*pending further purification

8
13C NMR spectrum of the cellulose mixed ester (acetate-hexanoate ester) in CDCl3
(DSacet= 1.5, DShex= 0.6)
13C-NMR SPECTRUM OF CELLULOSE
ACETATE HEXANOATE

9
13C CP/MAS NMR spectra of
the cellulose esters (Upper:
hexanoate ester, DS 0.7
Lower: laurate ester, DS 1.0 )
13C-CP/MAS NMR SPECTRA OF
CELLULOSE LAURATE & HEXANOATE

10
13C-NMR SPECTRUM OF MIXED
ANHYDRIDE

11
CHARACTERISATION OF
THERMOPLASTICITY
Acetate laurate 180
°C
Extruded strand
Pressed in hot press
+ Plasticiser
Melt compounding in
mini compounder
Created with NETZSCH Proteus software
[#] Type
[1.1] Dynamic
Range
35°C/10.0(K/min)/105°C
Acq.Rate
100.00
STC
1
P2:N2
40.0
PG:N2
20.0
Vac
0
P1:--
0.0
Corr.
DSC:020, TG:020
[#] Type
[1.2] Isothermal
Range
105°C/00:40/105°C
Acq.Rate
25.00
STC
1
P2:N2
40.0
PG:N2
20.0
Vac
0
P1:--
0.0
Corr.
DSC:020, TG:020
Project :
Identity :
Date/time :
Laboratory :
Operator :
Sample :
Fubio Cellulose
W LL VI-185B
6.3.2014 19:20:28
BA315.
MN
W LL VI-185B, 8.935647 mg
Material :
Correction file :
Temp.Cal./Sens. Files :
Sample car./TC :
Mode/type of meas. :
Segments :
Tausta 050314.ngb-bs1
130814 - Final Control NETZSCH.ngb-ts1 / 130814 - Final Control NETZSCH.ngb-es1
DSC/TG Octo S / S
DSC-TG / sample with correction
5
Crucible :
Atmosphere :
TG m. range :
DSC m. range :
Pre Mment Cycles :
DSC/TG pan Al2O3
-- / N2 / N2
5000 mg
5000 µV
2xVac
Instrument : NETZSCH STA 449F1 STA449F1A-0226-M File : C:DataProjektitFubio SelluloseW LL VI-185B.ngb-ds1 Remark : Initial mass: 8,936
0 5 10 15 20 25 30 35 40 45
Time /min
0
50
100
150
200
250
Flow /(ml/min)
85
90
95
100
105
TG /%
-0.25
-0.20
-0.15
-0.10
-0.05
0.00
0.05
0.10
0.15
DSC /(mW/mg)
30
40
50
60
70
80
90
100
110
Temp. /°C
Additional 1 2014-03-17 14:59 User: prommn
[1.1] WLL VI-185B.ngb-ds1
TG
DSC
Flow (purge2: N2)
Flow (protective: N2)
Temp.
[1.2] WLL VI-185B.ngb-ds1
TG
DSC
Flow (purge2: N2)
Flow (protective: N2)
Temp.
10 °C/min to +105 °C + isothermal 40 min
Residual Mass: 99.7 % (105.0 °C)
[1.1]
[1.1]
[1.1]
[1.1]
[1.1]
[1.2]
[1.2]
[1.2]
[1.2]
[1.2]
↑ exo
TGA / DSC
melting point,
glass transition temperature
Hot press
Acetate laurate

12
• Domsjö (enz. treatment), Acetic
anhydride, Lauric acid, DS total 2.5
• Domsjö (mech. treatment) Acetic
anhydride DS 2 , Lauric acid DS 0.5
Melting
Very brittle
White
Homogenous
Melting
Brittle
Non-homogenous
Slightly transparent
MELTING EXPERIMENTS

13
Cellulose Mw
Sigma α-cellulose 670k
Borregaard 1700k
Domsjö after mechanical disintegration 570k
Domsjö (enzyme treated) 350k
Cellulose acetate butyrate 350k
Acid-catalyzed acetate laurate 30k
Acetate laurate in high consistency n/a, but > 30k
MELTING EXPERIMENTS - CONCLUSIONS
- Molar mass of the material makes a difference both in chemical modification and
viscosity of the melt  Borregaard derivatives do not melt  acid-catalyzed
derivatives have a low viscosity and low molar mass  optimum viscosity is
required for processing
- Purity problems with WLL-samples
- Sigma α-cellulose forms nice melts, but the material has been commercially
homogenized  higher expenses

14
TGA / DSC CELLULOSE ACETATE
LAURATE
Finnish Bioeconomy Cluster FIBIC Oy 22.9.2017
• Melting and degradation temperatures are close to each other and operating window
is not wide (similar to certain cellulose acetates)
• Plasticising improves the thermoplasticity and decreases the melting / softening
temperature
• Properties are quite close to cellulose acetates and higher quantity of fatty acid groups
are needed than initially thought
Tg at 199 °C (onset)
Melting at 304 °C (peak)
10 w-% degraded at 328 °C
Degradation at 370 °C (peak)
50 100 150 200 250 300 350 400 450 500
Temperature /°C
-5
-4
-3
-2
-1
0
DSC /mW
10 °C/min to 900 °C
in nitrogen
[1.1] Acet3Laur.ngb-ds1
DSC
DSC
Peak: 57.0 °C
Peak: 303.9 °C
198.8 °C
200.4 °C
200.4 °C
201.7 °C
Glass Transition:
Onset:
Mid:
Inflection:
End:
[1.1]
[1.3]
↑ exo
200 300 400 500 600 700 800
Temperature /°C
20
40
60
80
100
TG /%
-30
-20
-10
0
10
DTG /(%/min)
10 °C/min to 900 °C
in nitrogen
TG (subtr.3)
DTG (subtr.3)
-10 % TG
Peak: 370.4 °C
365.9 °C
Mass Loss (Marsh):
Mid:
Value: 105.0 °C, 99.7 %
% Temp. Search:
89.7 %
328.2 °C
Residual Mass: 9.3 % (899.7 °C)
[1.3] TG (subtr.3)
[1.3] DTG (subtr.3)

15
MELT-SPINNING OF COMMERCIAL CA AND
CAB
Requirements for melt spinning
• Narrow melting peak
• Thermal stability at spinning temperature
(slightly higher than melting point)
• Suitable molar mass (and melt viscosity)
• Plasticizer not necessarily needed for CAB
(depending on the molar mass)
Polymer Spinning
temp (⁰C)
Take-up
speed
(m/min)
Hot draw
ratio
Linear
density
(dtex)
Tenacity
(cN/dtex)
Elongation
(%)
CA 225 30 - 175±22 0.3±0.1 38±32
CAB 220 800 - 7.1±1.7 1.2±0.2 19±5
CAB 220 200 - 6.0±1.5 0.7±0.1 791±30
CAB - - 1:7 1.0±0.3 4.6±0.5 54±5
CAB - - 1:10 0.7±0.2 6.4±1.0 27±6
PP 220 200 - 34 ±10 1.0±0.1 806±38
PP - - 1:6 6.4±1.0 6.2±0.3 49±11
Result: CAB is comparable to PP!
Results by Marja Rissanen et al. TUT

16
16
Good quality film,
but no adhesion to
the substrate;
coating layer totally
loose
Johanna Lahti, Hanna Christophliemk et al.
Pilot scale extrusion coating trial at TUT

17
CONCLUSIONS
- Melt-spinning and extrusion coating of commercial cellulose acetate butyrate is
possible even on larger scale and high-quality materials can be produced
- The low cost, high consistency modification method developed in this project does
not lead to equally high quality materials unless cellulose is homogenized 
Commercial materials have a higher cost for a reason
- The content of the fatty acid groups in the cellulose acetate laurates has to be
higher than initially evaluated  yet there is a clear possibility to use cellulose
acetate laurates commercially  homogenization of cellulose is still needed
- New ways to economically homogenize cellulose could lower the costs
substantially (mechanical activation, new solvents/chemical activation agents such
as deep eutectic solvents or recyclable ionic liquids)
FURTHER INFORMATION IN THE FIBIC FINAL
REPORT
THANK YOU!

Fibic thermoplastic cellulose final public seminar 15 4 2014

Recommended

Recommended

More Related Content

What's hot

What's hot (20)

Similar to Fibic thermoplastic cellulose final public seminar 15 4 2014

Similar to Fibic thermoplastic cellulose final public seminar 15 4 2014 (20)

Recently uploaded

Recently uploaded (20)

Fibic thermoplastic cellulose final public seminar 15 4 2014