1. Novel Hemicellulose Materials
Based on Wood Pulps
Ali Harlin, Harri Setälä
VTT Technical Research Centre of Finland

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VTT Industrial biomaterials
technology | applications | business
a growth oriented strategic VTT initiative
(person years of R&D per year):
75py/2009 125py/2013
combines multidisciplinary know-how of VTT:
biotechnology, nanotechnology, chemistry,
coating, pulp & paper, converting, construction,
process and value chain modeling,
strongly orientated towards break-trough
applications and renewing businesses

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Industrial biomaterials
Apply biochemical, process and material research on renewing industry in
the packaging, construction and appliances
On emerging customer oriented value-chains
Through high performing bio-mass based materials and products thereof
The biomass solutions, which do not compete with food production.
Biomass fractionation, metabolic engineering, enzymatic
Generic, grafting, catalytic and synthetic chemistry,
enabling
technologies Chemical engineering and modeling,
Compounding, extrusion, molding, coating, converting
LCA, delivery chain management design, customer solutions

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Polymers from biomass
Biopolymers from renewable raw materials
Modification and functionalization technologies (patented) for
tayloring the properties of biopolymers.
Applications
Derivatives and compositions for adhesives and hot melts.
Materials for injection moulding and extrusion coating
Binders for coatings, paints and adhesives.
Coatings and matrix materials for controlled release of active
ingredients.
Organic pigments and nanoparticles.

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Hemicellulose dispersions for barriers
Technology:
VTT has proprietary technology on fraction, in-situ modification
and cross-linking of natural polymers and especially
hemicellulose.
Features and benefits:
Internally softened hemicellulose with markedly more moisture stabile
than starch.
Glass transition temperature has been adjusted between 42…136 oC.
Improved film forming properties and thermoplasticity.
Barrier performance OTR = 5-15 cm3/m2/day, WVTR = 40-60
g/m2/day.
Application technologies:
Dispersion coating for board and corrugates.
Useful also in biopolymer compounds.

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Soluble xylan derivatives
The novel xylan derivatives were prepared based on proprietary
technology:
These xylan derivatives formed totally transparent and flexible
OTR
films.
PE = 8750
PLA = 900 NEXT: Application studies as films, barriers and soluble binders
PET = 180 in coating as well as mechanical properties have started.
=> Xylan is good
osAX (40% OTR OP
plasticizer) 0 months 0 months
osAX (gly) 11.8 ± 0.2 5.4 ± 0.3
osAX (gly:sor 3:1) Broken Broken
osAX (gly:sor 1:1) 10.2 4.1
osAX (gly:sor 1:3) 9.0 ± 0.4 3.1 ± 1.1
osAX (sor) 11.8 ± 5.0 3.7 ± 2.0
6

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The Finnish Centre of Excellence in White Biotechnology – Green Chemistry Research
RESEARCH OF NOVEL BIOBASED POLYMER
PLATFORMS
O O O
O O O
O O O O O O
OH OH
HO HO
OH HO
To research and evaluate O O O O O
O
• sugar acid and
• hydroxy acid based NH
O
green chemical synthesis of OH
HO
• monomers and O
OH
• polymers NH
forming selected platforms for
• hydrogel, O O O O O
O
• primers, and OH OH
HO
OH OH OH
• latexes O O O O O O
enabling development of sustainable products O
O
O
O
O
O

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The Finnish Centre of Excellence in White Biotechnology – Green Chemistry Research
Hydrogel platfom
Background: Hydrogels are material platform for superabsorbents and smart polymers,
essential in several applications like hygenic products and health-care materials
Objective: To develop sustainable replacements for non-biodegradable acrylates.
Challange: Efficient green synthesis routes to sugar monomers efficient in hydrogels
Comparison of different polysaccharides as starting materials for 1200% hydrogel preparation
thrpugh high OH and/or NH2 group intent
Epoxide based crosslinkers – sufficient hydrogel strength
Biotechnically produced aldonic acid (mono acid) derivatives as monomers in novel polymers
HO O
NH3+
HO O
HO
NH3+
OH
O OH
NH3+ H

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The Finnish Centre of Excellence in White Biotechnology – Green Chemistry Research
Why to study sugar acids and polysaccharides as starting
materials for novel hydrogels and superabsorbents?
Hydrogels are threedimensional crosslinked structures formed by hydrophilic polymers. They can
absorb large amounts of water depending e.g. on pH or ionic strength of the solution.
Modified aldaric acids such as their diallyldiamide derivatives may be used as crosslinkers in
hydrogels, e.g. N,N’-diallyltartardiamide is already commercially available. These products are
related to the widely used crosslinker methylene bisacrylamide (MBA).
Polysaccharides are hydrophilic natural polymers which can be used as promising starting materials
for hydrogels and/or superadsorbents, e.g. cellulose, xylan, or galactoglucomannan, and their
derivatives such as hydroxypropyl cellulose or carboxymethylcellulose.
1. Biopolymer-based microgels/nanogels for drug delivery applications; Oh et al. Progr. Polym. Sci. 34 (2009) 1261–1282.
2. Novel crosslinking methods to design hydrogels, Hennink and Nostrum Adv. Drug Deliv. Rev. 54 (2002) 13–36.
3. Enhancing molecularly imprinted polymer binding properties via controlled/living radical polymerization and reaction analysis, Vaughan et al. Polymer 48 (2007)
74-81.
4. New dextrin-vinylacrylate hydrogel: Studies on protein diffusion and release, Carvalho et al. Carbohydr. Polym. 75 (2009) 322–327.

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Acetylation of galactaric (mucic) acid
To protect hydroxyl groups in functionalization of carboxylic acid groups and in
polymerization
Performed in larger scale with Jucheim 2l reactor
Modified starch acetylation method with p-TsOH as catalyst
Easy purification by recrystallization from water
Yield ~50 % pure product
Biotechnically produced galactaric acid,
which is simple to recover
-OAc
1, 2,3
4

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Hydroxyl functional monomer from acetylated galactaric acid:
Synthesis of 2,3,4,5-tetra-O-acetyl-galactar-bis[(2-
hydroxyethyl)amide]
Procedure:
An amide salt is formed and crystallized from water
Refluxion if toluene at 120 oC for 3 h resulted the product
Use:
For polyester synthesis

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The Finnish Centre of Excellence in White Biotechnology – Green Chemistry Research
Preparation of hydrogels
N,N´-diallylaldardiamides as crosslinkers
Hydroxypropylated and allylated/butylated
derivative of xylan was crosslinked
(ds=0,3; 0,7 or 1 for allyl substituent)
Crosslinking was performed with UV-light
Potassiumpersulfate was used as
fotoinitiator
1 or 5 weight-% of crosslinker
Gel formed after a few minutes
O
Gels washed with H2O to remove any O O
unreacted material HO O
OH
O
O O n
Synthesis and Photocrosslinking Reaction of N-Allylcarbamoylmethyl O
Cellulose Leading to Hydrogel, Shen et al. Polymer Bulletin 56 (2006)137– HO O
143. O O
Synthesis and Preparation of Crosslinked Allylglycidyl Ether-Modified Starch- OH
Wood Fibre Composites, Duanmu et al. Starch/Stärke 59 (2007) 523–532. O
ds=1

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Current research in hydrogels
an example from literature
Hydrogels from acetylated galactoglucomannan via UV induced
radical polymerization using e.g. allylderivatives as crosslinkers
Voepel, J., J. Polym. Sci.: Part A: Polym. Chem., 47 (2009)
3595

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Voepel, J. et al. J. Polym. ds = 0,15 Current research in hydrogels
Sci.: Part A: Polym. Comparison of hydrogel swelling properies
Chem., 47 (2009) 3595
Swelling test (5 m-% crosslinker)
ds = 0,32
300
250
ds = 0,48 200 28. LA
29. T
ds/%
150 30. X
31. A
100 32. G
50
0
0 50 100 150 200 250 300 350
t/min
- Gel that has the lowest degree of substitution -All have a degree of substitution 0,7
absorbs the most (galactoglucomannan) - Starting material hardwood hemicellulose
- No added crosslinker - With crosslinker

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Properties of hydrogels
Swelling tests (DS 0,3)
Sw elling test (1 m -% crosslinker)
700
600
2g LA
degree o f sw elling %
500
LA
400
X
No crosslinker
LA = starting
300 material without T
200 crosslinker A
T, X, A, G =
100 G
crosslinkers
0
0 60 120 180 240
t / m in
Degree of swelling=(wet gel-dry gel)/dry gel*100
With crosslinker (1 m-%)

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Some examples of (active) stimuli and responses
Stimulus / input: Response / output:
temperature Reversible size or phase transitions
light
Electric current Changes of electric conductivity
Magnetic field Reological properties
Sound, vibration, oscillation discoloration
pH Changes of light transmission
moisture Etc.
pressure, torsiton, stretching
etc.
1. Memory materials 7.Piezoelectric materials
-metals -ceramic
Smart, intelligent, stimuli- -polymers -polymeric
sensitive, environmentally 2. Phase transition polymers 9. Colour changing materials
sensitive, functional, active 3. Auxetic materials
10. Polymergels, hydrogels
materials 4. Magnetorheological fluids
11. Conductive polymers
5. Electrorheological fluids
6. Magnetostrictive materials 12. Biologically active materials
-metals 13. Optic materials
-polymercomposites

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pH and thermoresponsive polymers
Polymers: alkylated poly(acrylamides) like PNIPAM
(poly-N-isopropylacrylamide); alkyl celluloses,
Poly(methyl vinyl ether); block co-polymers of ethylene
oxide etc.
Stimuli: pH, T, p, ionic strengh, solvent, chemical agents
etc.
Response: reverse phase transition, LCST, volume
change, enthalpy change (DH)
For instance, PNIPAM: Lower Chitical Solution
Temperature (LCST) 32-38 oC. The phase transition
range and LCST can be adjusted within + 5 … + 90 oC.
The range can be broad or narrow.
Volume change can be multifold (5 -1000 times)
Hydrophobic interactions vs. hydrogen bonding: The polymer chains show an expanded conformation
in water below the LCST due to strong hydration (hydrogen bonds) and changes to compact forms
above the LCST by dehydration (hydrophobic interactions exist).

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Membrane example
NIPA-PVA on a fabric
DH 65 J/g,
LCST 32-34 oC

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Results from VTT smart filter projects
Coating with stimuli-responsive polymers demonstrated for many industrial filter fabrics
such as PET, PP, PVA, and cellulose
Coatings are chemically stable in broad process conditions: pH 3-12, temperature 0 – 80
oC.
Adjusment of LCST using copolymerization demonstrated in the range 20 oC to 70 oC.
Smart, stimuli-responsive phenomenon and polymers approved to improve washing of
fouled filter materials: saving of energy and chemicals.
Possible to apply the developed coating technology for many different kind of fibres,
materials and applications.
The main are results published: Pirkonen, P., Setälä, H., Kyllönen, H., Sarlin, J., Salo, K., Tenhu, H., Ruuskanen, P., Thermal
Stimuli Controlled Functional Filter Cloth For Liquid Filtration, Filtration 10(2) 2010, 144-152.
Patent application: FI 117272 B, Suodatin, menetelmä sen valmistamiseksi ja sen käyttö / Filter, förfarande för framställing
därav och dess använding

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Stimuli-responsive cellulose membrane
Membranes are needed for
• Efficient fractionation
• Novel processes
• Dialysis
at 40 oC it turns
• from solid to slightly white,
• transparent, soft, and flexible
Simultaneously transparency is changed

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VTT creates business from
technology