Novel Hemicellulose MaterialsBased on Wood PulpsAli Harlin, Harri Setälä VTT Technical Research Centre of Finland
24/05/2011 2 VTT Industrial biomaterials technology | applications | businessa growth oriented strategic VTT initiative(person years of R&D per year): 75py/2009 125py/2013combines multidisciplinary know-how of VTT:biotechnology, nanotechnology, chemistry,coating, pulp & paper, converting, construction,process and value chain modeling,strongly orientated towards break-troughapplications and renewing businesses
24/05/2011 3 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, enzymaticGeneric, grafting, catalytic and synthetic chemistry,enablingtechnologies Chemical engineering and modeling, Compounding, extrusion, molding, coating, converting LCA, delivery chain management design, customer solutions
24/05/2011 4 Polymers from biomass Biopolymers from renewable raw materials Modification and functionalization technologies (patented) fortayloring 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.
24/05/2011 5 Hemicellulose dispersions for barriersTechnology: 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.
24/05/2011 6 Soluble xylan derivatives The novel xylan derivatives were prepared based on proprietary technology: These xylan derivatives formed totally transparent and flexibleOTR films.PE = 8750PLA = 900 NEXT: Application studies as films, barriers and soluble bindersPET = 180 in coating as well as mechanical properties have started.=> Xylan is goodosAX (40% OTR OPplasticizer) 0 months 0 monthsosAX (gly) 11.8 ± 0.2 5.4 ± 0.3osAX (gly:sor 3:1) Broken BrokenosAX (gly:sor 1:1) 10.2 4.1osAX (gly:sor 1:3) 9.0 ± 0.4 3.1 ± 1.1osAX (sor) 11.8 ± 5.0 3.7 ± 2.0 6
24/05/2011 7The 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
24/05/2011 8The Finnish Centre of Excellence in White Biotechnology – Green Chemistry Research Hydrogel platfomBackground: Hydrogels are material platform for superabsorbents and smart polymers,essential in several applications like hygenic products and health-care materialsObjective: 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
24/05/2011 9The 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.
24/05/2011 10 Acetylation of galactaric (mucic) acidTo protect hydroxyl groups in functionalization of carboxylic acid groups and inpolymerizationPerformed 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
24/05/2011 11 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 productUse: For polyester synthesis
24/05/2011 12The 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
24/05/2011 13 Current research in hydrogels an example from literatureHydrogels 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
24/05/2011 14Voepel, J. et al. J. Polym. ds = 0,15 Current research in hydrogelsSci.: Part A: Polym. Comparison of hydrogel swelling properiesChem., 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
24/05/2011 15 Properties of hydrogels Swelling tests (DS 0,3) Sw elling test (1 m -% crosslinker) 700 600 2g LAdegree 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 inDegree of swelling=(wet gel-dry gel)/dry gel*100 With crosslinker (1 m-%)
24/05/2011 16 Some examples of (active) stimuli and responsesStimulus / 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 -polymericsensitive, environmentally 2. Phase transition polymers 9. Colour changing materialssensitive, 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
24/05/2011 17 pH and thermoresponsive polymersPolymers: alkylated poly(acrylamides) like PNIPAM(poly-N-isopropylacrylamide); alkyl celluloses,Poly(methyl vinyl ether); block co-polymers of ethyleneoxide etc.Stimuli: pH, T, p, ionic strengh, solvent, chemical agentsetc.Response: reverse phase transition, LCST, volumechange, enthalpy change (DH)For instance, PNIPAM: Lower Chitical SolutionTemperature (LCST) 32-38 oC. The phase transitionrange 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 conformationin water below the LCST due to strong hydration (hydrogen bonds) and changes to compact formsabove the LCST by dehydration (hydrophobic interactions exist).
24/05/2011 18Membrane example NIPA-PVA on a fabric DH 65 J/g, LCST 32-34 oC
24/05/2011 19 Results from VTT smart filter projectsCoating with stimuli-responsive polymers demonstrated for many industrial filter fabricssuch as PET, PP, PVA, and celluloseCoatings are chemically stable in broad process conditions: pH 3-12, temperature 0 – 80oC.Adjusment of LCST using copolymerization demonstrated in the range 20 oC to 70 oC.Smart, stimuli-responsive phenomenon and polymers approved to improve washing offouled 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., ThermalStimuli 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 framställingdärav och dess använding
24/05/2011 20Stimuli-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
24/05/2011 21VTT creates business fromtechnology