23rd annual meeting of the Bio-Environmental Polymer Society

October 12-15, 2015 Karlsruhe, Germany

Content Schedule of lectures………………………………………………………………1 List of posters………………………………………………………………………9 Abstracts of lecures………………………………………………………………11 Abstracts of posters………………………………………………………………56

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Program

Lectures and Posters

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Monday, October 12, 2015 Registration will open 10.00 am

10.50 – 12.30 Session 1 (chair: Michael Meier) 10.50 – 11.00 Welcome and opening remarks 11.00 – 11.45 High-added-value materials with cellulose nanocrystals Christoph Weder, Adolphe Merkle Institute, Switzerland 11.45 – 12.30 Innovative solutions for renewable polymers

Niklas Meine, Bayer MaterialScience AG (Covestro as of 01.09.2015), Germany

12.30 – 14.00 Lunch break 14.00 – 15.40 Session 2 (chair: Christoph Weder) 14.00 – 14.25 Modification of starch-blends with PLA by using a novel one-

step compounding process Johannes Fuchs, Institute of Material Engineering, Polymer

Engineering, University of Kassel, Germany 14.25 – 14.50 Tailoring the porosity of bacterial cellulose nanopapers by

solvent inclusion Andreas Mautner, Polymer and Composite Engineering (PaCE)

group, University of Vienna, Austria 14.50 – 15.15 Softwood hemicelluloses function as novel sustainable

emulsion stabilizers Kirsi S. Mikkonen, University of Helsinki, Finland 15.15 – 15.40 Influences of fiber homogenization on production and

processing of fibrillated cellulose suspensions Pieter Samyn, University of Freiburg - Freiburg Institute for

Advanced Studies, Germany 15.40 – 16.10 Coffee break

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16.10 – 17.40 Session 3 (chair: Henri Cramail) 16.10 – 16.55 Towards greener materials: Wood adhesives based on

hemicellulose and Nanolatexes for hydrophobization of biofibers Linda Fogelström, Royal Institute of Technology (KTH), Stockholm, Sweden

16.55 – 17.40 Novel renewable coating resins based on limonene oxide and CO2

Cor Koning, Eindhoven University of Technology and DSM, The Netherlands

18.00 – 21.00 Poster session with buffet dinner and drinks Posters will be displayed until the end of the conference

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Tuesday, October 13, 2015 09.00 – 10.35 Session 4 (chair: Stuart Coles) 09.00 – 09.45 Polyesters from biogenic aromatics

Stephen Miller, University of Florida, US 09.45 – 10.10 Development of furfural-based polymers Yuya Tachibana, Gunma University and JST PRESTO, Japan 10.10 – 10.35 A new generation of (bio)degradable polyesters based on 2,5-

furandicarboxylic acid Andreia F Sousa, CICECO-University of Aveiro, Portugal 10.35 – 11.05 Coffee break 11.05 – 12.55 Session 5 (chair: Cor Koning) 11.05 – 11.30 Development of smart bionanocomposites based on PLA by

chemical grafting of nanopolysaccharides Sandra Domenek, INRA, Ingénierie Procédés Aliments – AgroParisTech, France

11.30 – 11.55 PHB/NFC blends for composite and coating applications

Pieter Samyn, University of Freiburg - Freiburg Institute for Advanced Studies, Germany

11.55 – 12.20 Experimental studies of marine coral (cuttlebone) reinforced

polymer composites Garje Channabasappa Mohankumar, National Institute of Technology, Karnataka (NITK SURATHKAL), India

12.20 – 12.45 A comparative view on the performance profile of laminated paper-thermoplastic composites

Christoph Burgstaller, Transfercenter für Kunststofftechnik GmbH, Wels, Austria

12.45 – 12.55 Award Ceremonies 12.45 – 14.15 Lunch break

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14.15 – 15.25 Session 6 (chair: Luc Averous) 14.15 – 15.00 Adding the green side to a petro-chemical evergreen

Matthias Ullrich, Evonik Industries AG

15.00 – 15.25 Towards an expansion of the renewable feedstock for the synthesis of functional and degradable polymers Karin Odelius, KTH Royal Institute of Technology, Stockholm Sweden

15.25 – 15.55 Coffee break 15.55 – 17.30 Session 7 (chair: Alexander Bismarck) 15.55 – 16.40 Selective catalysis using bio-derived epoxides, carbon

dioxide, anhydrides and lactones: preparation and properties of multi-block copolymers

Charlotte Williams, Imperial College London, UK

16.40 – 17.05 Carbon dioxide-based thermo-plastics and PLA based Bio-Screws

Hyun-Joong Kim, Seoul National University, Korea 17.05 – 17.30 Confinement of PLLA by layer multiplying co-extrusion: effect

on microstructure and on gas barrier properties Alain Guinault, PIMM, Arts et Métiers ParisTech, Paris, France

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Wednesday, October 14, 2015 09.00 – 10.35 Session 8 (chair: Matthias Ullrich) 09.00 – 09.45 Innovative aliphatic-aromatic biobased polyurethanes from

different biomass Luc Averous, BioTeam/ICPEES-ECPM, Strasbourg, France

09.45 – 10.10 A new way of creating cellular polyurethane materials: NIPU

foams Adrien Cornille, ENSCM, Montpellier, France

10.10 – 10.35 Thermo-responsive non-isocyanate polyurethanes through

Diels-Alder adduct polymerization Elena Dolci, ENSCM, Montpellier, France

10.35 – 11.05 Coffee break 11.05 – 13.05 Session 9 (chair: Stuart Coles) 11.05 – 11.50 Plant oil chemistry: what can be done beyond?

Chuanbing Tang, University of South Carolina, US

11.50 – 12.15 A modified Wacker Oxidation process: efficient oxyfunctionalization of fatty acid derivatives Marc von Czapiewski, Karlsruhe Institute of Technology (KIT), Germany

12.15 – 12.40 Effect of methanol-fractionated Kraft lignin on gas barrier

properties of poly(3-hydroxybutyrate-co-3-hydroxybalerate) thin films Adriana Kovalcik, Institute for Chemistry and Technology of Materials, Graz University of Technology, Austria

12.40 – 13.05 Sustainable and environmentally friendly allylation of

Organosolv Lignin Lena Charlotte Over, Karlsruhe Institute of Technology (KIT), Germany

13.05 – 14.30 Lunch break

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14.30 – 16.05 Session 10 (chair: Chuanbing Tang) 14.30 – 15.15 Crossing the biomass feed-stocks for novel bio-sourced

polymers Henri Cramail, LCPO, University of Bordeaux, France

15.15 – 15.40 New fully biobased macromolecular architectures: analysis of

the structure-property relationships of synthesized copolyesters from building blocks

Thibaud R Debuissy, Strasbourg University, France 15.40 – 16.05 Composite models for compression moulded cellulose fibre-

reinforced brittle thermoplastics Nina Graupner, Bremen City University of Applied Sciences,

Germany 16.30 BEPS business meeting 19.00 Conference dinner: Badisch Brauhaus

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Thursday, October 15, 2015 09.00 – 10.30 Session 11 (chair: Stephen Miller) 09.00 – 09.45 Non-isocyanate polyurethanes for greener foams and plastics

Andrew W Myers, Kansas Polymer Research Center, US

09.45 – 10.30 Biodegradable and renewable polymers: How to contribute to a sustainable future? Carsten Sinkel, BASF, Germany

10.30 – 11.00 Coffee break 11.00 – 12.40 Session 12 (chair: Linda Fogelström) 11.00 – 11.25 Direct and efficient polymerization of levulinic acid via Ugi

multicomponent reaction Manuel Hartweg, Queen Mary University of London, UK

11.25 – 11.50 Tailored isohexide monomers by catalytic isomerisation &

amination Rebecca Pfützenreuter, RWTH Aachen University, Germany

11.50 – 12.15 Influence of biopolymers on the recycling of conventional

plastics Blanca M. Lekube, Transfercenter für Kunststofftechnik GmbH 12.15 – 13.45 Lunch break 13.45 – 15.40 Session 13 (chair: Charlotte Williams) 13.45 – 14.30 Replacing styrene in thermoset polyesters

Stuart R Coles, University of Warwick, UK 14.30 – 15.15 Biopolymers to make emulsions and using Them as injectable

scaffolds

Alexander Bismarck, University of Vienna, Austria 15.15 – 15.30 closing remarks

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Posters

P1 Evaluation of environmental degradability of poly(butylene n-alkylene

dicarboxylate)s Takuro Baba, Yuya Tachibana, Shota Suda, Ken-ichi Kasuya, University of Gunma, Japan

P2 Extraction of Betula Pendula with an ionic liquid

Veronika Strehmel1, David Strunk1, Nadine Strehmel2, 1Niederrhein University, Germany, 2Leibniz Institute of Plant Biochemistry, Germany

P3 Cyclic organic carbonates as oxyalkylating reagents for lignin

Isabell Kühnel, Bodo Saake, Ralph Lehnen, University of Hamburg, Germany P4 Synthesis of modified polycaprolactams based on renewable resources

Stefan Oelmann, Michael A. R. Meier, KIT, Germany P5 Consolidated bioprocessing for production of polyhydroxyalkanotes by co-

culture of Sacchraophagus degradans and Bacillus cereus from complex polysaccharides Shailesh S. Sawant, Bipinchandra K. Salunke, Beom Soo Kim, Chungbuk National University, South Korea

P6 Modified β-cyclodextrin obtained from Ugi five-component reactions with

carbon dioxide Rebekka Schneider, Felix Mack, Michael A. R. Meier, KIT, Germany

P7 Biodegradable polymeric biomaterials based on aliphatic bipolyesters for

medical application Michał Kwiecień, Marek Kowalczuk, Grażyna Adamus, Polish Academy of Science, Poland

P8 Biodegradable polymeric system for controlled release of bioactive

substances Iwona Kwiecień, Tomasz Bałakier, Janusz Jurczak, Iza Radecka, Marek Kowalczuk, Grażyna Adamus, Polish Academy of Sciences, Poland

P9 Synthesis of isocyanate free urethanes with hydroxyl groups based on

synthetic and renewable resources Katrin Mathea, Annett Halbhuber, Arunjunai Raj Mahendran, Uwe Müller, Bernd Strehmel, University Niederrhein, Germany

P10 Renewable high Tg polymers via a novel Biginelli polycondensation

Andreas C. Boukis, Michael A. R. Meier, KIT, Germany P11 Towards greener epoxy resins based on waste frying oil

Felipe C Fernandes, Kerry Kirwan, Maria Sotenko, Stuart Coles, University of Warwick, UK

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P12 Determination of antioxidant activity of new biobased macrobisphenols Armando Reano, Florent Allais, Anne-Marie Riquet, Sandra Domenek, AgroParisTech, France

P13 Synthesis, characterization, biological properties and polymerizations of new

bio-based macrobisphenols derived from ferulic acid Armando Reano, Florent Allais, Florian Pion, Oulame Mouandhoime, Sandra Domenek, Paul-Henri Ducrot, Tiphaine Clement, AgroParisTech, France

P14 Thermal properties of cellulose acetate blends with thermoplastic urethanes

and plasticizers Rafael Erdmann, Stefan Zepnik, Stephan Kabasci, Hans-Peter Heim, Fraunhofer Society, Germany

P15 Synthesis of plant oil derived, long-chain polyethers via GaBr3-catalyzed

reduction of fatty acid derived carboxylic acid esters Patrick-Kurt Dannecker, Ursula Biermann, Jürgen O. Metzger, Michael A. R. Meier, KIT, Germany

P16 Green chain – shattering polymers based on a self-immolative azobenzene

motif Hatice Mutlu, Christopher Barner-Kowollik, KIT, Germany

P17 Sustainable derivatization of cellulose with diallyl carbonate

Zafer Söyler, Felix Poschen, Michael A. R. Meier, KIT, Germany P18 Renewable, fluorescent and thermoresponsive: Cellulose copolymers via

cellulose functionalization in ionic liquids and RAFT-polymerization Andrea Hufendiek, Christopher Barner-Kowollik, Michael A. R. Meier, KIT, Germany

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Abstracts

Part 1: Lectures

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L1

High-added-value materials with cellulose nanocrystals

Christoph Weder, Adolphe Merkle Institute, Switzerland

Cellulose nanocrystals (CNCs) are attracting growing interest as inexpensive and

renewable components that are useful for the creation of a broad variety of nanomaterials.

This presentation will discuss several examples of advanced materials in which the CNCs

provide a high added value. The ability to switch the interactions between (surface-

modified) CNCs in polymer matrices has allowed the design of mechanically adaptive

nanocomposites, and is also useful to reinforce healable polymers. The possibility to

create functional high surface area materials can be utilized for fluorescence-based

sensing schemes. The high surface area and the possibility to chemically anchor a

payload can also be exploited for CNC-based pro-fragrances; in this case, the CNCs are

decorated with fragrance molecules using a short, labile linker, which serves to covalently

connect the fragrance molecules with the nanocarrier and promotes slow release of the

payload. Finally, the fabrication of multi-layer polymer nanocomposite tissue engineering

scaffolds that mimic the structural design, chemical cues, and mechanical characteristics

of mature articular cartilage is presented. In part due to the surface chemistry of the CNCs,

these scaffolds guide the morphology, orientation, and phenotypic state of cultured

chondrocytes in a spatially controlled manner, support the growth of tissue with features

that are reminiscent of the natural analogue, and promote localized hydroxyapatite

formation to permit integration with the subchondral bone.

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L2

Innovative solutions for renewable polymers

Niklas Meine, Gernot Jäger, Berta Vega Sánchez, Bayer MaterialScience AG (Covestro as

of 01.09.2015), Germany

The increasing world population will have a strong impact on the global demand for energy

and feedstocks that are also used to produce fuels, chemicals and polymers. Today, most

of the chemicals used in the polymer industry are based on fossil feedstock, but renewable

raw materials are gaining importance.

Polymers derived from renewable raw materials show the potential to reduce greenhouse

gas emissions by (i) saving fossil resources, (ii) realizing more environmental benign

production processes, and (iii) using plant based raw materials that took up CO2 during

photosynthesis. As an example, some processes like biotechnological fermentations work

at low temperatures and produce less waste. In this way, already today some bio-based

chemicals (e.g. succinic acid) are being produced cost efficiently on large scale. Covestro

is interested in these renewable chemicals that are more sustainable than their petro-

based counterparts, lead to high-performance products and are long-term cost efficient.

Bio-based chemicals are commonly produced by biotechnological or chemo-catalytic

conversion of renewable feedstocks like saccharides. Covestro’s innovation team is

evaluating such technologies already at an early development stage in order to identify the

potential of upcoming renewable chemicals. Therefore, Covestro is working with leading

partners along the value chain to develop the production of these chemicals, use them for

product developments and, finally, bring high-performance products to the market.

For a long time Covestro already used renewable monomers for its polymer production.

Thereby, the company focused in the past on bio-based polyols for polyurethanes, which

are conceived for various applications such as building insulation, cold chain and piping

insulation, mattresses or sport shoes. Typically, natural oils like castor- and soya oil, or

sugars and glycerol are raw materials from which polyether polyols are being produced. In

the last years, Covestro has developed further bio-based polyols that can also be used for

making polyurethanes but are based on upcoming biobased chemicals such as succinic

acid.

Recently, Covestro has developed pentamethylene diisocyanate (PDI) - a new milestone

in polyurethane chemistry - an entirely new isocyanate, 70 percent of whose carbon

content comes from biomass without generating any direct competition for food production.

The first bio-based polyurethane crosslinker based on this novel molecule has been

launched: Desmodur® eco N 7300. This is the first plant-based aliphatic polyurethane

hardener to be used for coatings, adhesives and other applications. Commercial

manufacturing of the first bio-based PDI-product is planned for 2016 and the

manufacturing will be carried out in existing plants using energy efficient gas-phase

technology.

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L3

Modification of starch-blends with PLA by using a novel one-step compounding process

Johannes Fuchs, Maik Feldmann, Hans-Peter Heim, Institute of Material Engineering,

Polymer Engineering, University of Kassel, Germany

Native starch is a suitable raw material for the synthesis of bioplastics (i.e., PLA), or as a

filler for thermoplastic materials owing to its low costs. However, the compounding and

injection molding processes must be modified to process native starches. Moreover, the

hydrophilic properties necessitate a drying of the material before processing. The

hydrophilic characteristics also restrict the number of fields in which starch blends can be

applied. In order to make these materials able to compete with comparable materials, an

enhancement of the mechanical properties is compulsory.

By means of newly developing, or tailoring the preparation and processing methods, it is

possible to modify the starch, and, thus, increase the number of application fields in which

it can be employed. Amongst others, Epichlorohydrin has been used to crosslink native

starches. One disadvantage of Epichlorohydrin is its toxicity. Due to this handicap, starch-

blends modified with Epichlorohydrin are limited in their areas of application (i.e., food

packaging). Another option as reagent to modify native starch is nonhazardous

Glycidylether. This cross-linking agent even shows a high reactivity at low temperatures

using a catalyst. Up to now, several process steps are required to dry, modify and blend

native starch with PLA. Due to time and cost expenditures it is necessary to improve the

compounding process (fewer process steps) to make starch-blends competitive.

In the first instance, native starch was modified in a two-step process. Therefore the starch

was crosslinked using a laboratory mixer. Subsequently, the previously modified starch

and PLA were compounded using a co-rotating twin screw extruder. In the injection

molding process, the blends were processed into samples. In order to determine the

influence of the modification and process control on the hydrophobization and material

properties of the starch blends, the materials were then examined regarding their

thermomechanical and structural properties. Compared to conventional starch blends, the

modified starch made in the two-step process exhibited higher mechanical properties.

Following, a novel one-step compounding process was developed by using a customary

co-rotating twin screw extruder.

The crosslinking in the native starch resulted in an increase in the mechanical properties

(tensile strength, impact strength etc.) of the starch blends. Blends with a content of 50

weight percent starch show even higher mechanical properties than unfilled PLA.

Furthermore, the blends with crosslinked starch display lower levels of moisture absorption

according to blends with native starch.

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L4

Tailoring the porosity of bacterial cellulose nanopapers by solvent inclusion

Andreas Mautner1, Koon-Yang Lee2, Alexander Bismarck3, 1Polymer and Composite

Engineering (PaCE) group, University of Vienna, Austria, 2Department of Aeronautics, Imperial College London, UK, 3Polymer and Composite Engineering (PaCE) group,

Imperial College London, UK

Treatment of waste water for the removal of contaminants is an important task in order to

fight the problem of water shortage, which is already a significant issue in many regions of

this planet. As pollutants are present at almost all length scales, from large particles in the

mm range down to microbes on the micro and nano-scale, different technologies are

required. For the purpose of removing contaminants on the nano-scale, nanofiltration (NF)

or tight ultrafiltration (UF) membranes have been developed. These membranes are

predominantly made of synthetic polymers derived from fossil resources that require

significant amounts of chemicals and energy during their manufacture. In addition, they

constitute a serious waste problem after use. Therefore, utilization of membranes based

on renewable resources, such as nanocellulose papers, could be a vital alternative.

Cellulose papers have a long tradition as filter and membrane material dating back to

ancient times. However, conventional filter papers, produced from cellulose microfibrils,

exhibit certain limitations when pollutants in the nanometer range are to be removed.

Using a conventional paper making process utilizing cellulose microfibrils fails to produce

papers capable of UF or even NF operations. Recently, we demonstrated the utility of

nanocellulose and bacterial cellulose papers, also often referred to as nanopapers, as tight

aqueous UF membranes by application of a papermaking process. Unfortunately, the

permeance of these membranes is limited, which is connected to a relatively high density

resulting in low porosity.

To target this drawback, it is assumed that producing nanopapers from dispersions of BC

in organic solvents rather than water should give rise to a change in density and thus

porosity of BC nanopapers. This enhancement in overall porosity, based on the

phenomenon of “solvent inclusion”, is proposed to significantly enhance the permeance of

BC papers but without sacrificing the pore size and thus the efficiency of the membrane.

We here present nanopapers made from bacterial cellulose from a set of different types of

organic solvents through a simple paper making process via solvent inclusion that exhibit

unchanged pore size but increased permeability and thus efficiency due to increased

porosity.

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L5

Softwood hemicelluloses function as novel sustainable emulsion stabilizers

Kirsi S. Mikkonen, Claire Berton-Carabin, Chunlin Xu, Karin Schroën, University of Helsinki, Finland

O-Acetyl-Galactoglucomannans (GGM) are sustainable polysaccharides abundantly

available in softwoods and their mechanical pulp, from which they dissolve in the process

water of industrial mills and can be isolated at high yield and purity. Recent efforts on

GGM research are focused on their recovery from modern forestry biorefining processes

and utilization in, e.g., material, packaging, or biomedical applications. GGM are known to

stabilize the colloidal dispersions of wood-derived lipophilic substances in pulp fibers. We

study the potential of GGM as stabilizers in food systems, which could be suitable novel

applications for these plant-based polysaccharides. In the present study, GGM and their

carboxymethyl derivatives (CM-GGM) were dissolved in aqueous buffer solution and used

as the continuous phase of rapeseed oil-in-water emulsions (5 wt.-% oil, 0.01–1 wt.-%

GGM or CM-GGM), prepared by high pressure homogenization using a microfluidizer.

The oil droplet size distribution was followed during four weeks of storage at room

temperature, using static light scattering. In addition, the zeta potential (ζ) of emulsion

droplets was determined and the morphology of emulsions was investigated by optical

microscopy. The partitioning of GGM and CM-GGM between the continuous phase and on

the oil-water interface was investigated after separating the emulsions’ phases by

centrifugation. GGM and CM-GGM greatly enhanced the emulsion formation compared to

plain buffer solution, and produced oil droplets with average diameter (d3,2) of about

400 nm. The visual appearance of the emulsions as well as the droplet size distribution

over storage revealed that GGM and CM-GGM efficiently stabilized the emulsions against

physical breakdown. The mechanisms of stabilization of the model food emulsions by

GGM and CM-GGM will be discussed.

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L6

Influences of fiber homogenization on production and processing of fibrillated cellulose suspensions

Pieter Samyn, Vibhore Rastogi, University of Freiburg - Freiburg Institute for Advanced Studies, Germany

Cellulose fibers are well-explored for the formulation of reinforced bio-based composites,

as they are abundantly available and can be obtained from a variety of natural sources,

including wood and plants. The fibers are hierarchically structured with the subsequent

alignment of microfibrils, elementary fibrils and cellobiose units as ordered in crystalline

and amorphous zones. From nanotechnological point of view, the fibrillated cellulose has

received high interest because of their dense fibrous network structure and consequently,

barrier properties and mechanical strength. In this work, the homogenization of hardwood

cellulose pulp into several degrees of fibrillation has been further optimized by selection of

the production parameters and number of processing steps of the pulp suspension in a

microfluidizer, inducing micro- to nanoscale fibrillation of the fibers by internal shear.

Especially, preliminary homogenization of the suspension has shown significant influences

on the fiber morphology, followed by alternating production cycles through finer interaction

chambers of 200 µm and 87 µm diameter under different pressures. The morphologies

and surface charges of the resulting fibers have been quantified by AFM and Zetapotential

measurements and correlated to rotational and oscillatory rheometry data. The

experimental test design was first optimized to exclude effects of wall slip by selecting an

appropriate gap distance. Furthermore, relations between rheology and fiber morphology

are drawn. The rheological data for samples after homogenization show clear packing

within the ramp up under steady state shear test, while good stability after fibrillation

occurs over a broad range of processing parameters. After further homogenization, the

initial gel-type characteristics turn into the behavior of dilute suspension depending on the

degree of defibrillation.The NFC has pseudoplastic and thixotropic behaviors under low

shear rate conditions and dilatant behavior under high shear rate conditions. In parallel,

increasing of temperature and shear rate decreases viscosity of NFC dispersions

tremendously. This can be related to variations in network density and fiber interaction.

With use of Herschel Bulkley model, a relation between the yield stress and processing

conditions was found.

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L7

Towards greener materials: Wood adhesives based on hemicellulose and Nanolatexes for hydrophobization of biofibers

Linda Fogelström, Emelie Norström, Linn Carlsson, Anna Carlmark, Eva Malmström,

Royal Institute of Technology (KTH), Stockholm, Sweden

Increased environmental awareness is a strong motivation for many of the research

activities at the Division of Coating Technology at KTH Royal Institute of Technology to be

focused on sustainable solutions, from a materials perspective. These activities are

exemplified by the following two projects: “Wood adhesives based on hemicellulose” and

“Nanolatexes for hydrophobization of biofibers”. Wood adhesives are mainly prepared from

polymers derived from petroleum-based resources. With the increasing concern for the

environment, it is necessary to find alternatives derived from bio-based resources that can

replace petroleum-based polymers. To enable this transition it is important that the

adhesive properties in terms of bond strength, water resistance and heat resistance are

similar, and that the alternative can compete in terms of cost. Motivated by the wood-

biorefinery concept of using side-streams from the forest-products industry, and by the

promising results from our previous studies on other polysaccharides in this type of

applications,[1] we are now investigating the possibilities for using hemicelluloses from

wood as binders in wood adhesives. Water dispersions of xylan were prepared and

evaluated. However, xylan itself cannot be used as a wood adhesive due to its limited

bonding performance, especially regarding the water resistance. Therefore, the addition of

dispersing agents, poly(vinyl alcohol) or poly(vinyl amine), and crosslinkers, such as

glyoxal or hexa(methoxymethyl) melamine, were evaluated. Several of the xylan

dispersions demonstrate good bond strength and surprisingly good water and heat

resistance when gluing wood veneers; especially xylan together with a relatively small

amount of poly(vinyl amine) shows remarkable water resistance and bond strength.[2]

The pulp and paper industry has for centuries modified cellulose by polyelectrolyte

adsorption, in order to improve properties such as wet-strength and de-watering. This

approach is especially advantageous for the modification of nanocelluloses, such as

cellulose nanofibrils (CNF), as these are produced in dilute water suspension and can

easily be anionically charged through TEMPO-oxidation. By utilizing controlled

polymerization techniques, more advanced polyelectrolytes can be obtained, allowing the

possibility for fine-tuning the properties of the surfaces of cellulose fibers and fibrils.[3]

Herein, cationic polymer latexes have been prepared and physically adsorbed to cellulose

model surfaces and cellulose nanofibrils (NFC). Charged polymer nanoparticles composed

of amphiphilic block copolymers based on poly(dimethylaminoethyl methacrylate)

(PDMAEMA) and a hydrophobic block composed either of a high Tg polymer, poly(methyl

methacrylate) (PMMA), or a low Tg polymer, poly(butyl acrylate) (PMA), were synthesized

by RAFT-mediated[4] surfactant-free emulsion polymerization. During the synthesis, the

amphiphilic block copolymers self-assembled into spherical cationic latex nanoparticles by

polymerization-induced self-assembly (PISA).[5] These cationic latexes were then

19

physically adsorbed onto cellulose model surfaces and CNF. From adsorption

measurements in the QCM-D, it was shown that large amounts of latex-particles were

adsorbed to the cellulose-model surfaces, something which was also confirmed by AFM

measurements. The surfaces were fairly hydrophobic after the adsorption and upon heat

treatment of the surfaces, which collapsed the latex particles and exposed the hydrophobic

core, the hydrophobicity increased.

[1] E. Norström, L. Fogelström, P. Nordqvist, F. Khabbaz, E. Malmström, Ind. Crops Prod.

2014, 52, 736

[2] E. Norström, L. Fogelström, P. Nordqvist, F. Khabbaz, E. Malmström, E. Eur.Pol. J.

2015, 67, 483

[3] A. Carlmark, Macromol. Chem. Phys., 2013, 14, 1539

[4] C. Barner-Kowollik, Handbook of RAFT-polymerization. 2008, Wiley-VCH.

[5] B. Charleux, G. Delaittre, J. Rieger, and F. D'Agosto, Macromolecules, 2012, 45, 6753

20

L8

Novel renewable coating resins based on limonene oxide and CO2

Cor Koning, Chunliang Li, Rafael Sablong, Theo Veldhuis, Bart Reuvers, Eindhoven

University of Technology and DSM, The Netherlands

α,ω-Dihydroxyl poly(limonene carbonate)s (PLCs) were synthesized by copolymerization

of limonene oxide with CO2, using a β-diiminate zinc-bis(trimethylsilyl)amido complex as

the polymerization catalyst,[1] followed by transcarbonation reactions using various

(metallo)organic catalyst/polyol systems. The structure and end groups of the PLCs were

identified by MALDI-ToF-MS. The α,ω-dihydroxyl PLCs were evaluated as renewable

coatings after solvent casting and curing with polyisocyanates. However, the partly tertiary

hydroxyl end groups resulted in incomplete curing and merely moderate coating

properties. More promising curing results were obtained for PLCs with pendant primary

OH groups, introduced by thiol-ene chemistry onto the pendant double bonds.[2] The best

coating performance was achieved upon using thiol-ene curing chemistry, involving the

pendant double bonds of the PLC and a trifunctional thiol compound, either by thermal or

by photochemical initiation. The latter approach was both applied to solvent-borne and

powder coatings.

[1] M. Cheng, D.R. Moore, J.J. Reczek, B.M. Chamberlain, E.B. Lobkovsky, G.W. Coates,

J. Amer. Chem. Soc. 2001,123, 8738

[2] C. Li, R. Sablong, C.E. Koning, Eur. Polym. J. 2015, 449

21

L9

Polyesters from Biogenic Aromatics

Stephen Miller, University of Florida, US

Cellulosic bioethanol processes, applied presently to corn and experimentally to

sugarcane, yield lignin-rich waste streams. Extraction of these cellulosic bioethanol waste

streams for valuable phytochemicals, such as ferulic acid and coumaric acid. has been

demonstrated. These phytochemicals have many direct uses, including vitamin

supplements and anti-oxidant food additives, as well as downstream uses as building

blocks for sustainable polymers that can replace water bottle plastic (PET) and

Styrofoam™ (PS). The Miller Research Group has developed novel methods for

synthesizing linear thermoplastic polymers from lignocellulose phytochemicals. These

thermoplastics will be discussed in the context of replacing traditional, fossil fuel-based

plastics. Key to their commercialization is the symbiosis between academic innovation

and a recent start-up company, U.S. Bioplastics (http://usbioplastics.com).

22

L10

Development of Furfural-Based Polymers

Yuya Tachibana, Masayuki Yamahata, Saori Kimura, Koji Nagayama, Ken-ichi Kasuya,

Gunma University and JST PRESTO, Japan

As social demand for renewable sources of commodity plastics has increased, biomass

has attracted much at-tention as a promising alternative to petrochemicals. The resources

used to produce biobased plastics should be inedible, waste, and abundant. Furfural is an

ideal biomass resource, as it is traditionally produced from cellulosic and waste biomass

such as corncob, corn stock, and rice hull. Furthermore, it is extremely abundant, with a

global output of 500,000–1,000,000 tonne/year. The US Department of Energy (DOE) has

stated that it is one of the most value-added chemicals derived from biomass. Another

advantage of using furfural is that it can be readily converted to other useful chemicals due

to its high reactivity. Furfural is in-dustrially converted to furan via decarboxylation and has

been used as a source of bio-fuels. In this presentation, we introduce the synthesis of

biobased monomers derived from furfural and furan via chemical process, and its

polymerization to biobased polymers.

1. Synthesis of Telephtalic Acid (TPA) toward Poly(ethylene terephthalate) (PET)[1]

PET resin is a widely used commodity plastic with applications in fibre manufacture,

packaging, and elec-tric devices. Coca-Cola Ltd. and other beverage com-panies have

adopted biobased-PET since 2009 when they announced that their containers would

change from petroleum-based PET to biobased PET. However, this commercially

available biobased PET is composed of bio-ethylene glycol derived from bio-ethanol, and

petroleum-based terephthalic acid (TPA) made from p-xylene produced by fractional

distillation of naphtha. Consequently, its percentage biomass carbon content, as defined

below, is a mere 20%. The development of a route to biobased TPA would allow the

synthesis of fully biobased PET, an extremely attractive prospect from both economic and

environmental viewpoints.

We reported a synthetic route for the production of TPA from furfural. Furfural was

oxidised and dehy-drated to give maleic anhydride, which was further reacted with

biobased furan to give its Diels-Alder (DA) adduct. The dehydration of the DA adduct gave

phthalic anhydride, which was converted via phthalic acid and dipotassium phthalate to

TPA. The biobased carbon content of the TPA was measured by accelera-tor mass

spectroscopy and the TPA was found to be made of 100% biobased carbon.

2. Development of Poly(oxabicyclate)s as Novel high Performanced and Biodegradable

Polyesters

We thought that it is possible to convert only the com-pounds produced from furfural into

more complex compounds. The DA adducts with reactive groups (i.e. a double bonded

moiety, a dicarboxylic anhydride moiety and a bulky oxabicyclic (OBC) alkene). Hy-

drogenation of the double bond prevents the retro-DA reaction of the double bond and an

OBC alkene and produces a thermally stable OBC dicarboxylic anhy-dride (OBCA).

23

We reported the preparation of biobased oxabi-cyclic dicarboxylic anhydride derived from

furan de-rivatives and its polymerization with several α,ω-diols to polyoxabicyclates. 1H

NMR spectra and MAL-DI-TOF MS measurements verified the chemical structure of the

polyoxabicyclates (POBC)s. POBC prepared using 1,3-propanediol or 1,4-butanediol could

be moulded into elastic films by melt pressing. Tensile strength testing of the films

indicated that they were highly elastic. The films had good transparency in the visible

region. Furthermore, POBCs had good biodeg-radability.

[1] Y. Tachibana, S. Kimura, K. Kasuya, Sci. Rep., 2015, 5, 8249 .

[2] (a) Y. Tachibana, M. Yamahata, K. Kasuya, Green Chem., 2013, 15, 1318 . (b) Y.

Tachibana, M. Yamahata, H. Ichihara, K. Kasuya, submitted. (c) Y. Tachibana, M.

Yamahata, S. Kimura, K. Kasuya, submitted. (d) Y. Tachi-bana, K. Nagayama, K. Kasuya,

submitted.

24

L11

A new generation of (bio)degradable polyesters based on 2,5-furandicarboxylic acid

Andreia F Sousa1, Marina Matos1, Ana C. Fonseca2, Carmen S. R. Freire1, Jorge F. J. Coelho2, Armando J. D. Silvestre1, 1CICECO-University of Aveiro, Portugal, 2CEMUC,

University of Coimbra, Portugal

Polymer research based on renewable feedstocks has emerged in recent years with a renewed strength, motivated essentially by the pertinent demand for sustainable alternatives to non-renewable fossil plastics.

In this vein, 2,5-furandicarboxylic acid based polyesters emerged in the polymer scene has some of the most valuable alternatives.[1] In particular poly(ethylene 2,5-furandicarboxylate) (PEF),[2] due to its resemblance to the well-known poly(ethylene terephthalate) (PET) is today one of the most promising renewable-based polyesters. However, PEF lacks in biodegradability, indeed turning furan-based polyesters (bio)degradable, while maintaining their high performance properties, is a huge challenge which is worthwhile pursuing.

The present study[3] was precisely conducted with the specific aim of developing novel materials with enhanced biodegradability. In this perspective, a logical approach was to copolymerise PEF with a (bio)degradable aliphatic precursor which would introduce (bio)degradability properties to the ensuing copolyesters. Poly(lactic acid) (PLA) due to its high versatility, (bio)degradability and biocompatibility (besides being an aliphatic polyester obtained from renewable feedstocks) was the selected aliphatic counterpart. These copolyesters have been synthesised by polytransesterification reactions and characterised in detail.

PEF-co-PLA copolyester incorporating only 8% of lactyl units showed to have enhanced biodegradability compared both to PEF and to PET, and at the same time displayed very high degradation and glass transition temperatures (c.a. 324 and 76 oC, respectively) like its PEF homologue.

The properties PEF-co-PLA open the way to the development of an entirely new generation of commodity polymers based on renewable resources bearing promising (bio)degradability. Indeed, more recently, along with the same aim, novel unsaturated polyesters resins incorporating in their backbone both furanic units and variable percentages of unsaturated aliphatic units were also synthetised by bulk polycondensation, followed by thermal curing. They showed high performance thermo-mechanical properties, and they are potentially biodegradable.

Acknowledgements:

The authors wish to thank the project CICECO-Aveiro Institute of Materials (Ref. FCT UID

/CTM /50011/2013), financed by national funds through the FCT/MEC and when

appropriate co-financed by FEDER under the PT2020 Partnership Agreement.

25

[1] A. F. Sousa, C. Vilela, A. C. Fonseca, M. Matos, C. S. R. Freire, G.-J. M. Gruter, J. F.

J. Coelho, A. J. D. Silvestre. Polym. Chem. 2015.

[2] A. Gandini, A. J. D. Silvestre, C. Pascoal Neto, A. F. Sousa, M. Gomes, J. Polym. Sci.

Polym. Chem. 2009, 5, 295.

[3]) M. Matos, A. F. Sousa, A. C. Fonseca, C. S. R. Freire, J. F. J. Coelho, A. J. D.

Silvestre, Macromol. Chem. Phys. 2014, 215, 2175.

26

L12

Development of smart bionanocomposites based on PLA by chemical grafting of nanopolysaccharides

Sandra Domenek1, Etzael Espino-Perez1, Giana Almeida-Perré1, Julien Bras2, INRA, Ingénierie Procédés Aliments – AgroParisTech, France, LGP2/Grenoble INP, France

In recent years, much attention has been focused on biodegradable and biocompatible

polymers, particularly from an ecological viewpoint. Polylactide (PLA) has been attracting

great attention, because it is producible from renewable natural sources, such as corn,

wheat, sugar beet. PLA is a good candidate for food packaging because it can be

converted by conventional polymer processes, it has a good transparency like PET.

However, its drawback is its poor gas barrier properties. To modulate the polymer barrier

properties, many strategies have been developed like crystallization, biaxial streching, co-

extrusion and more recently the crystallization under confinement.[1]

The layer multiplying co-extrusion process can be used to confine polymer.[2] In this way,

pairs of immiscible polymers can be fabricated into an unlimited length of nanolayered

films having layers less than 10 nm in thickness. Starting with the co-extrusion of a two (A-

B) or a three (A-B-A) layers assembly and by adjusting the number of multiplying

elements, it is possible to create films with tens, hundreds or thousands of alternating

nanometric layers.

In this work, the PLA (PLLA) was confined by poly(styrene) (PS). Ten multiplying elements

(2049 layers) were used in order to reach theoretically 20 nm continuous thick layer of

PLLA between theoretically 60 nm thick layer of PS in final 100 μm thick films. Continuous

PLLA nano-layers, down to 20 nm of thickness were obtained with the processing protocol

used. Helium and oxygen permeability results did not highlight an effect of PLLA

confinement (comparaison of a bulk PLLA film with a confined PLLA nanolayer). But an

unexpected improvement factor was obtained by annealing at 85°C the PLLA confined

nanolayers compared to the annealed bulk PLLA. Thermal analysis and X-ray

measurements are in progress to understand these results and to try to correlate with the

crystalline and the amorphous phases microstructures.

[1] H. Wang, JK. Keum, A. Hiltner, E. Baer. Macromolecules, 2009; 42: 7055.

[2] F. Ania, FJ. Baltá-Calleja, A. Flores, GH. Michler, S. Scholtyssek, D. Khariwala, A.

Hiltner, E. Baer, L. Rong, BS. Hsiao. European Polymer Journal, 2012; 48: 86.

27

L13

PHB/NFC blends for composite and coating applications

Pieter Samyn, Vibhore Rastogi, University of Freiburg - Freiburg Institute for Advanced Studies, Germany

The benefits of poly(hydroxybutyrate) as biopolymer for packaging applications are

attributed to its good barrier properties with low permeability for O2, H2O and CO2. The

PHB has better oxygen barrier properties than both PP and PET and water vapour barrier

properties than PP. The physical and mechanical properties are comparable to those of

isotactic polypropylene. As a main drawback, the material is relatively stiff and brittle

compared to traditional polymers, which is generally attributed to its crystallization

behaviour: the low nucleation density results in the formation of large spherulites, which

contain crazes and initiates splitting. Moreover, secondary crystallization (i.e. progressive

conversion of amorphous to crystalline material over time) occurs during storage at room

temperature, forming new lamellae in the amorphous phase. These drawbacks can be

surpassed by better control of the crystallization process, which is generally achieved by

copolymerization, e.g. in PHB-HV or P(3HB-4HB). In another route, nanotechnology may

influence the crystallization process, where nanoscale additives are introduced as

nucleating agents.

In this work, the mechanical properties of PHB and its barrier properties are further

enhanced by adding several types of microfibrillated cellulose (MFC) and nanofibrillated

cellulose (NFC) into PHB. Therefore, a novel batch formulation process has been

developed for the fabrication of PHB/NFC and PHB/MFC master batches that are

transformed into films by hot pressing. The content of MFC and NFC could be varied in

percentages ranging from 0.25, 0.50, 0.75, 1, 2 and 5 %, resulting in homogeneous films

without aggregation. After monitoring the crystallization by thermal analysis and polarized

microscopy, efficient enhancement of the crystallization kinetics and formation of small

spherulite structures have been detected in presence of nanofillers. In parallel, one type of

modified MFC (mMFC) with hydrophobic surface properties has been added. The

variations in modulus of elasticity and elongation for the different PHB nanocomposite

films have been investigated, showing enhancement in elongation and strength for

PHB/NFC compared to the native PHB films. Otherwise, the surface-modified MFC shows

highest improvement in modulus of elasticity together with a decrease in elongation, which

confirms the good improvement in interface compatibility.

28

L14

Experimental studies of marine coral (cuttlebone) reinforced polymer composites

Garje Channabasappa Mohankumar, Kamal Babu Periasamy, National Institute of

Technology, Karnataka (NITK SURATHKAL), India

Marine corals are mainly composed of calcium carbonate and organic matrix; those can be

used as filler in polymer composites thus consequential in waste utilization of aquaculture

waste-products. In the present study, raw cuttlebone particles (CB), heat treated

cuttlebone particles (HB) as well as commercial calcium carbonate particles (CC)

reinforced in epoxy resin (EP) matrix. Different forms of reinforcement materials were

characterized by thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy

(XPS) to confirm the polymorph transformation. Thermal stability and glass transition

temperature of EP, EP/CB, EP/HB and EP/CC composites were investigated by TGA and

differential scanning calorimetry (DSC). EP/CC composite had highest glass transition

temperature than EP, EP/CB and EP/HB composites, but EP/CB and EP/HB has good

thermal stability than EP and EP/CC composites. Tensile tests were carried out to

determine the composites strength and compared with predefined theoretical models.

Heat-treated cuttlebone reinforced epoxy composites showed higher tensile properties and

better interaction between filler and matrix than other composites. Experimental results of

HB/EP composites showed constant improvement in tensile modulus with increasing filler

content, thus indicating adequate adhesion between filler and matrix. HB/EP and CB/EP

composites had superior tensile strength than the CC/EP composites (at 9 wt%), because

of good interaction between cuttlebone filler and polymer matrix. Experimental results

reveal that, the cuttlebone particles reinforced polymer composites are very promising

material.

29

L15

A comparative view on the performance profile of laminated paper-thermoplastic composites

Christoph Burgstaller1, Martina Prambauer1, Christian Paulik2, 1Transfercenter für

Kunststofftechnik GmbH, Wels, Austria, 2Johannes Kepler University Linz

Composites are a widespread group of materials nowadays, because these can fulfil

performance profiles which are typically not reached with the single constituents. Problems

associated with classical composites, based on inorganic fibres like glass or carbon and

thermosetting materials are the end of life scenarios, although such composites show

superior performance. Over the last decade, intensive research was carried out to

substitute the thermosetting part with thermoplastics, therefore getting the possibility to

carry out some mechanical recycling of such composites for another life cycle. Anyway,

the fibre component still is problematic due to the high input of energy to produce glass or

carbon fibres. Therefore, the aim of this work is to elaborate on the performance of

laminated paper thermoplastic composites in comparison to inorganic reinforced as well

as natural fibre based structural composites. Therefore, composites with different weight

fractions, based on a thermoplastic matrix, here polypropylene (chosen as the initial

material because of the ease of working with it) as well as different reinforcements, e.g.

paper sheets, flax and glass fabrics were produced by a film stacking and hot pressing

method. From these composites, specimens were cut for tensile tests as well for

microscopic evaluation and density determination. The results show, that the paper based

composites materials yield values close to the ones of flax fabric reinforced. These are

lower than the test values for glass fabric reinforced materials, which is due to the fibre

properties on the one hand, but also due to the not optimized paper layers on the other

hand. Nevertheless, with a paper content of 50 vol% one yields an elastic modulus of

about 6 GPa and a tensile strength of 70 MPa, which are sufficient for many applications in

rigid packaging and transportation applications. Further works here deal with the

optimisation of the composite build up in regard to paper grade and content, to yield even

higher property profiles, utilisable in transportation applications.

30

L16

Adding the green side to a petro-chemical evergreen

Matthias Ullrich, Evonik Industries AG

Polyamide 12 (‘PA12’) is a long-established specialty polymer. It embodies a uniquely

balanced set of physical and chemical properties, the foundation for the high performance

of the materials based on it. Thus it is trusted in a wide variety of demanding application

fields. Evonik is the only commercial supplier of PA12 that boasts a fully back-integrated

production, as it starts making PA12 from a petro-chemical commodity, being butadiene.

Setting the trend in polyamides again, Evonik now develops a new route towards PA12,

unparalleled in its conciseness, and second-to-none technologically advanced. Beyond

today’s petro-approach, the new route starts from a renewable source, commercial methyl

laurate (lauric acid methyl ester, ‘LAMe’), a direct derivative of palm kernel oil (‘PKO’). It

then utilizes a key bio-chemical transformation to convert LAMe in a single-step

fermentation process into the monomer to PA12, i.e. the omega-functional long-chain

amino acid, 12 Amino lauric acid (‘ALA’).

Both bio-based and bio-produced, Evonik’s ALA thus constitutes a true “bio-analogue” to

the “classic” petro-monomer to PA12, laurolactame (‘LL’). Forwards, both ALA and LL yield

a PA12 material of identical bulk properties with respect to reference materials and

Evonik’s established product specifications.

Altogether, Evonik’s new route to PA12 distinguishes itself by more than just one

governing aspect: First and foremost, it indeed delivers a truly and fully bio-based polymer.

Second, moreover, its bio-chemical and bio-technological approach constitutes an industry

breakthrough how to functionalize fatty acids. Third, and ultimate to the markets, both

routes, petro and bio, deliver a PA12 identical by its technical specifications, yet with the

choice between product upstreams fully independent, whilst indiscriminatingly converging.

his contribution will outline Evonik’s development story of its new “bio PA12”. Focal points

will be a) the development philosophy and framework, b) the design of the cell and the bio-

chemistry happening within, c) the (bio)-technology of the fermentation process, d) the

polymerization of ALA to PA12, and e) the technology and intellectual property

differentiation.

31

L17

Towards an expansion of the renewable feedstock for the synthesis of functional and degradable polymers

Karin Odelius, KTH Royal Institute of Technology, Stockholm Sweden

With a growing focus on green materials, the array of monomers derived from renewable

resources for e.g. controlled polymerization (ring-opening or controlled radical

polymerization) needs to be further explored and an understanding of how their

macromolecular architectures translate into specific material properties needs to be

understood. Today’s availability in feedstock chemistry is limited to a few well known

monomers in commercially established plastics, restricting the diversity in material

properties. The unexploited potential in the chemistry of biobased and/or recycled

monomers that could be highly interesting for use in commercial production hence needs

to be expanded. Monomers presented here include: (i) biobased lactones produced in

large quantities by fermentation reactions e.g. ɛ-decalactone,[1,2] (ii) monomers synthesized

from a renewable feedstock by green approaches e.g. aliphatic carbonates,[3,4] and (iii)

monomers from waste streams e.g. crotonic acid produced by microwave induced

recycling of PHB.[5,6] By exploiting the diversity in the nature of these monomers and by

combining them with other functional monomers,[7] new and well-defined materials are

synthesized in a controlled way.[1-7]

The research leading to these results has received funding from the Swedish Research

Council, VR (Grant ID: 621201356 25), the ERC Advance Grant, PARADIGM (Grant

Agreement No.: 246776), and the European Union´s Seventh Framework Programme for

research, technological development and demonstration under Grant Agreement No.

311815

[1]. P. Olsén, T. Borke, K. Odelius, A.-C. Albertsson, Biomacromolecules, 2013, 14, 2883,

[2]. V. Arias, P. Oslén, K. Odelius, A. Höglund, A.-C. Albertsson, Polym. Chem., 2015, 6,

3271

[3]. P. Olsén, K. Odelius, A.-C. Albertsson, Macromolecules, 2014, 47, 6189

[4]. P. Olsén, K. Odelius, H. Keul, A.-C. Albertsson, Macromolecules, 2015, 48, 1703

[5]. X. Yang. K. Odelius, M. Hakkarainen, Sustainable Chem. Eng., 2014, 2, 2198

[6]. X. Yang, J. Clenet, H. Xu, K. Odelius, M. Hakkarainen, Macromolecules, 2015, 48,

2509

[7]. P. Olsén, J. Undin, K. Odelius, A.-C. Albertsson, Polym. Chem., 2014, 5, 3847

32

L18

Selective catalysis using bio-derived epoxides, carbon dioxide, anhydrides and lactones: preparation and properties of multi-block

copolymers

Charlotte Williams, Imperial College London, UK

The presentation will describe the synthesis and properties of new block copoly(ester

carbonates) which are partly/fully bio-derived. Recently, our group have developed a new

'switch' catalysis which enables a single homogeneous catalyst to function for both the

ring-opening polymerization of lactones and the ring-opening copolymerizaiton of

epoxides/anhydrides or epoxides/carbon dioxide.[1-4] Thus, it is now possible to selectively

polymerize mixtures of monomers so as to prepare (multi-)block copolymers.[2] The lecture

will describe the selective catalysis, highlighting the range of monomers which can be

polymerized using this technique. Several of the monomers are bio-derived and carbon

dioxide is also a suitable monomer for polycarbonate synthesis. Using the switch catalysis

allows the highly controlled preparation of (multi-)block copolymers. The properties of

these materials, including thermal and mechanical properties, will be presented.

References

[1] C. Romain, C. K. Williams, Angew. Chem. Int. Ed. 2014, 53, 1607.

[2] Y. Zhu, C.K. Williams, J. Am. Chem. Soc., 2015, 10.1021/jacs.5b04541

[3] S. Paul, Y. Q. Zhu, C. Romain, P. K. Saini, R. Brooks, C. K. Williams, Chem. Commun,

2015, 6459.

[4] Y. Zhu, C. Romain, V. Poirier, C. K. Williams, Macromolecules, 2015, 48, 2407.

33

L19

Carbon dioxide-based thermo-plastics and PLA based Bio-Screws

Hyun-Joong Kim, Ji-Won Park, Tae-Hyung Lee, Jung-Hun Lee, Pan-Seok Kim Seoul

National University, Korea

Currently, polymer technology, one step further of a basic roles, maximize facileness of

people and plays in providing opportunities that can coexist between mankind and natures.

Bio-plastics based polymeric materials have been studied from various viewpoints.

Particularly, around the PLA, various studied was promoted for its preparation and

application. Among them, bio-screw with biodegradable properties, led to innovations in

the medical industry. The screw allow new concept of the surgery that need no secondary

surgery. Carbon dioxide-based polymeric material, a new type of material which can be

expected the carbon capture & storage effects throughout the process of the synthesis and

its applications. PEC (polyethylene carbonate) and PPC (polypropylene carbonate) are

representative cases. These carbon dioxide-based polymer material has various limitation

in a single material, so many kinds of research are progressed to overcome the drawback.

34

L20

Confinement of PLLA by layer multiplying co-extrusion: effect on microstructure and on gas barrier properties

Alain Guinault1, Samira Fernandes Nassar2, Cyrille Sollogoub1, Nicolas Delpouve3, Sandra

Domenek2, Gregory Stoclet, 1PIMM, Arts et Métiers ParisTech, Paris, France, 2AgroParisTech, France, 3AMME-LECAP, Université de Rouen, France

In recent years, much attention has been focused on biodegradable and biocompatible

polymers, particularly from an ecological viewpoint. Polylactide (PLA) has been attracting

great attention, because it is producible from renewable natural sources, such as corn,

wheat, sugar beet. PLA is a good candidate for food packaging because it can be

converted by conventional polymer processes, it has a good transparency like PET.

However, its drawback is its poor gas barrier properties. To modulate the polymer barrier

properties, many strategies have been developed like crystallization, biaxial streching, co-

extrusion and more recently the crystallization under confinement.[1]

The layer multiplying co-extrusion process can be used to confine polymer.[2] In this way,

pairs of immiscible polymers can be fabricated into an unlimited length of nanolayered

films having layers less than 10 nm in thickness. Starting with the co-extrusion of a two (A-

B) or a three (A-B-A) layers assembly and by adjusting the number of multiplying

elements, it is possible to create films with tens, hundreds or thousands of alternating

nanometric layers.

In this work, the PLA (PLLA) was confined by poly(styrene) (PS). Ten multiplying elements

(2049 layers) were used in order to reach theoretically 20 nm continuous thick layer of

PLLA between theoretically 60 nm thick layer of PS in final 100 μm thick films. Continuous

PLLA nano-layers, down to 20 nm of thickness were obtained with the processing protocol

used. Helium and oxygen permeability results did not highlight an effect of PLLA

confinement (comparaison of a bulk PLLA film with a confined PLLA nanolayer). But an

unexpected improvement factor was obtained by annealing at 85°C the PLLA confined

nanolayers compared to the annealed bulk PLLA. Thermal analysis and X-ray

measurements are in progress to understand these results and to try to correlate with the

crystalline and the amorphous phases microstructures.

[1]. H. Wang, JK. Keum, A. Hiltner, E. Baer. Macromolecules 2009; 42, 7055.

[2]. F. Ania, FJ. Baltá-Calleja, A. Flores, GH. Michler, S. Scholtyssek, D. Khariwala, A

Hiltner, E. Baer, L. Rong, BS. Hsiao. European Polymer Journal 2012; 48, 86.

35

L21

Innovative aliphatic-aromatic biobased polyurethanes from different biomass

Luc Averous, BioTeam/ICPEES-ECPM, Strasbourg, France

The discovery of polyurethanes by O. Bayer and some coworkers in 1937, via the reaction

of a polyester diol with a diisocyanate, has permitted to develop a new family of valuable

polymers. With a production in 2011 of around 17,500 ktons/year and a market of 35

billions $, polyurethanes (PUs) is nowadays one of the most consumed family of polymers

in the world. They are widely used as paints, coatings, foams, adhesives and packaging

components in numerous fields such as automotive industry, consumer or domestic

equipment, construction engineering and biomedical applications. The performances and

properties of PUs are extensively tailored by the chemical nature of the reactants as well

as the processes used.

Nowadays, the use of renewable biobased carbon feedstock is highly taken into

consideration because it offers the intrinsic value of a reduced carbon footprint and an

improved life cycle analysis (LCA), in agreement with a sustainable development.

Polyurethanes are more and more often biobased, since polyols and polyisocyanates can

be biobased.[1-11] Various researches were particularly focused on biobased polyols (i)

from fermentation of biomass (white biotechnologies) or (ii) directly extracted from biomass

and then chemically modified, such as the oleochemical resources. Many industries

(BASF, Cargill, Croda, Huntsman, Oleon) now produce their own grades of biobased

polyols available in various ranges. Different works on biobased isocyanates were also

published but to a much lesser extent. The main raw materials are vegetable derivatives

(e.g., soybean oil, castor oil, and oleic acid). However, isocyanates from other renewable

resources such as isosorbide were also obtained. Some companies are currently

emerging in the industrial synthesis of biobased isocyanates such as Cognis (BASF-

Germany), which produce 2-heptyl-3,4-bis(9-isocyanatononyl)-1-pentylcyclohexane from a

dimer fatty acid, and Vencorex (Joint Venture between PTT Global Chemical – Thailand,

and the Perstorp Group), which commercialize an aliphatic polyisocyanate. All these

recent developments show that fully biobased PUs could be largely produced in a close

future, as recently shown by BAYER and BASF.

Most of the biobased PU are thermosets, however biobased TPUs (thermoplastics) have

been also developed.

However, biobased PUs do not mean health friendly products. In this way, the second

generation of environmental friendly PUs must also be non-toxic and health friendly, with a

low impact on the environment. Then conventional PUs must be modified and new

perspectives must be found. A new trend is emerging with the elaboration of non-

isocyanate polyurethanes (NIPUs), since isocyanates are harmful and suspected to be

36

carcinogen for humans. Different Biobased NIPUs have been elaborated in perfect

agreement with a green chemistry (e.g., without solvent, catalysts, ).[7]

In this presentation, we report an overview of more than 8 years of research @University

of Strasbourg (France), on the synthesis and characterization of several innovative and

bio-based polyurethanes (PUs, TPUs and NIPUs), with controlled and organized

macromolecular architectures.[1-11] They are synthesized with different biobased building

blocks: (i) aliphatic structures from modified glycerides, dimer fatty acids, sugar-based

molecules (isosorbide, ) … (ii) and aromatic structures from lignins, tannins and furans.

A large range of nice properties and durable applications can be developed from these

different architectures, for a greener and durable future.

E. Hablot, D. Zheng, M. Bouquey, L. Avérous , Macromolecular Materials & Engineering

2008, 293, 922.

C. Bueno-Ferrer, E. Hablot, M. C. Garrigós, S. Bocchini, L. Averous L., A. Jiménez,

Polymer Degradation and Stability 2012, 97, 1964.

C. Bueno-Ferrer, E. Hablot, F. Perrin-Sarazin, M. C. Garrigós, A. Jiménez, L. Averous,

Macromolecular Materials & Engineering 2012, 297, 777.

S. Laurichesse, L. Avérous, Polymer 2013, 54, 15, 3882.

S. Laurichesse, L. Avérous, Progress in Polymer Science 2014, 39, 1266.

S. Laurichesse, C. Huillet, L. Avérous Green Chemistry 2014, 16, 3958.

C. Carré, L. Bonnet, L. Avérous, RSC Advances 2014, 4, 54018.

M. Charlon, B. Heinrich, Y. Matter, E. Couzigné, B. Donnio, L. Avérous, European Polymer

Journal 2014, 61, 197.

A. Arbenz, L. Avérous, RSC Advances 2014, 4, 106, 61564.

A. Arbenz, L. Avérous, Industrial Crops and Products 2015, 67, 295.

A. Arbenz, L. Avérous, Green Chemistry 2015, 67, 2626.

37

L22

A new way of creating cellular polyurethane materials: NIPU foams

Adrien Cornille, Sylwia Dworakovska, Dariusz Bogdal, Sylvain Caillol, Bernard Boutevin,

ENSCM, Montpellier, France

The development of polyurethanes began in 1937 at I.G. Farbenindustrie where Bayer

with coworkers discovered the addition polymerization reaction between diisocyanates and

diols. Since their discovery, the demand in PUs has continued to increase and it will attain

in 2016 a production of 18 million tons[1] of which 75% are foams. However, isocyanates

compounds are harmful for human and environment. Methylene diphenyl 4,4’-diisocyanate

(MDI) and toluene diisocyanate (TDI), the most widely used isocyanates in PU industry,

are classified as CMR (Carcinogen, Mutagen and Reprotoxic). In order to design

isocyanate-free materials, an interesting alternative is the use of non-isocyanate

polyurethane (NIPU) by reaction between cyclic carbonate and polyfunctional amines.[2]

The main problem concerning NIPU synthesis relates to the low reactivity of

carbonate/amine reaction. Many studies in the literature have been conducted to design

NIPU materials from reactive cyclic-carbonates bearing electro-withdrawing substituent or

by using six-, seven membered or thio-cyclic carbonate. In order to improve the kinetics of

the carbonate/amine reaction, much research has been devoted to develop novel

catalysts. Blain et al.[3] and Lambeth et al.[4] showed that the 1,5,7-triazabicyclo[4.4.0]dec-

5-ene (TBD) and cyclohexylphenyl thiourea are the best catalysts for carbonate/amine

reaction. However, the reaction between carbonate and amine does not yield any gas,

therefore cannot lead to NIPU foam as easily as in the case of PUs. Moreover, to the best

of our knowledge, no literature has been published on the preparation of NIPU foams,

therefore, we aspired to synthesize the first NIPU foams as an original work. We chose

five-membered cyclic carbonates since their synthesis does not require any phosgene

derivative as in the case of six- or seven-membered cyclic carbonates. NIPU foams were

obtained by step growth polymerization of two types of five-membered cyclic carbonates,

in combination with aliphatic amines, one of it is derived from fatty acid dimerization. The

development of NIPU foams is a challenge which lies in the coordination of gelling reaction

(carbonate/amine reaction) and foaming reaction. We used

poly(methylhydrogenosiloxane) as blowing agent which reacts with amines, releasing

dihydrogen which allows to expand the NIPU materials. NIPU foams were characterized

by scanning electron microscopy, thermogravimetric analysis, differential scanning

calorimetry and by measurement density. The mechanical compression and the recovery

of these NIPU foams were analyzed by dynamic mechanical analyses at room

temperature.[5]

[1] O. Bayer, Angewandte Chemie 1947, 59, 257. [2] J. M. Whelan Jr., M. Hill, R. J. Cotter: US Patent 1963. [3] M. Blain, L. Jean-Gerard, R. Auvergne, D. Benazet, S. Caillol, B. Andrioletti, Green Chemistry 2014, 16, 4286. [4] R. H. Lambeth, T. J. Henderson, Polymer 2013, 54, 5568. [5] A. Cornille, S. Dworakowska, D. Bogdal, B. Boutevin, S. Caillol, Eur. Polym. J. 2015, 66, 129.

38

L23

Thermo-responsive non-isocyanate polyurethanes through Diels-Alder adduct polymerization

Elena Dolci, Rémi Auvergne, Bernard Boutevin, Sylvain Caillol, ENSCM, Montpellier,

France

Thermosetting polymers are widely used in coatings, composites and adhesives due to

their good mechanical and thermal properties. They cannot be shaped differently, or

processed, which means they cannot be recycled. This is a great deal for environmental

concern and as a result, remendable polymers have been widely studied over the last

decades.[1],[2] In particular, it has been pointed out that using remendable adhesives would

lead to a better recycling, especially for vehicles end-of-life or electronic waste.[3,4]

Polyurethanes (PUs) are widely used in adhesives as they are very versatile. In many

adhesives applications PUs are chemically cross-linked which make the resulting adhesion

irreversible. The aim is to break the crosslinked network in order to re-process it. The most

efficient way to obtain such polymer is to incorporate reversible bonds which can break on

demand. Temperature is the most practical stimulus and Diels-Alder (DA) adducts are

well-known and already studied in various works.[5],[6] Indeed DA reaction is a [4+2]

cycloaddition between a diene and a dienophile leading to an adduct which can dissociate

under thermal treatment to turn back to the previous diene and dienophile compounds

(rDA). Here the furane/maleimide couple is chosen as diene/dienophile because of their

good reactivity. Moreover, PUs are typically obtained by reaction between diisocyanates

and diols. As diisocyanates are harmful for human health and globally its environment, the

synthesis of non-isocyanate polyurethanes (NIPUs) has gained in interest in chemical

industry. The most promising alternative is the step-growth polymerization of

cyclocarbonates with amines.[7],[8] This original study is focused on the obtention of

thermoreversible NIPUs. An oligomeric dicyclocarbonate adduct is synthetized by DA

reaction and polymerized with a diamine. The challenge here lies in finding a compromise

between the low cyclocarbonate/amine reactivity and avoiding rDA reaction.

Polymerization was conducted at room temperature, using triazabicyclodecene (TBD) as a

catalyst. The final polymer is characterized and its thermal behavior investigated.

39

L24

Plant oil chemistry: what can be done beyond?

Chuanbing Tang, Liang Yuan, Zhongkai Wang, Nathan M Trenor, University of South

Carolina, US

Sustainable fuels, chemicals, and materials from renewable resources have recently

gained tremendous momentum in a global scale, although there are numerous nontrivial

hurdles for making them more competitive with petroleum counterparts. Plant oils stand

out as one of the most important renewable resources among rich raw materials and have

been widely used for the preparation of surfactants, intermediates, paints and resins, and

polymers and for the production of biofuels. Thus, efficient and economical transformation

of their major components, triglycerides, into simple fatty derivatives is highly sought for

further preparation of sustainable monomers, polymers, and materials. We recently

reported strategies for the preparation of oil based monofunctional monomers and

polymers using derivatives from the base-catalyzed amidation of plant oils. The amidation

process was achieved with nearly quantitative yields in the absence of column

chromatography, thus much appealing for sustainability. The subtle structural variation in

monomers has led to polymers with drastically different properties. In this presentation, we

will talk about our efforts on designing novel thermoplastics, thermoplastic elastomers and

advanced composite materials that are derived from plant oils.

[1] Z. Wang; L. Yuan; N. M. Trenor; F. E. Du Prez; C. Tang, Green Chem. 2015, 17, 3806.

[2] L. Yuan; Z. Wang; N. M. Trenor; C. Tang, Macromolecules 2015, 48, 1320.

40

L25

A modified Wacker Oxidation process: efficient oxyfunctionalization of fatty acid derivatives

Marc von Czapiewski, Michael A. R. Meier, Karlsruhe Institute of Technology (KIT),

Germany

The use of fats and oils as renewable feedstock in the field of organic synthesis and

especially for polymer chemistry has become ever more important during the last decades,

since these materials offer various application possibilities and a sustainable as well as an

economically attractive alternative to depleting fossil resources.[1] Moreover, the

development of processes using catalytic amounts of transition metals and stoichiometric

environmentally friendly oxidants, such as molecular oxygen, is one major goal in organic

chemistry. The Wacker Oxidation process has become one of the most important industrial

processes, as for instance demonstrated by manufacturing of acetaldehyde from ethylene.

Within this contribution, a modified Wacker Oxidation process was applied to achieve

ketone-functionalization of tryglycerides (e.g., olive oil) and thereof derived unsaturated

fatty acid methyl esters (e.g., methyl oleate, methyl linoleate) using a high pressure reactor

system.[2,3] For this purpose, catalytic amounts of palladium chloride were used in the

presence of a dimethylacetamide/ water mixture and either molecular oxygen or synthetic

air as re-oxidant. Furthermore, the catalytic system provides some advantages regarding

the sustainability, if compared to the original Wacker Oxidation process, since the

utilization of a co-catalyst (i.e., copper) can be avoided and dimethylacetamide can retain

the palladium catalyst in solution, which allows a straightforward recycling. Moreover, the

obtained ketone FAMEs represent an interesting class of starting materials for further

chemical modification, e.g., dimerization by reductive amination.

M. A. R. Meier, J. O. Metzger, U. S. Schubert, Chem. Soc. Rev. 2007, 36, 1788.

T. Mitsudome, K. Mizumoto, T. Mizugaki, K. Jitsukawa and K. Kaneda, Angew. Chem. Int.

Ed. 2010, 49, 1238.

M. Winkler, M. A. R. Meier, Green. Chem. 2014, 16, 1784.

41

L26

Effect of methanol-fractionated Kraft lignin on gas barrier properties of poly(3-hydroxybutyrate-co-3-hydroxybalerate) thin films

Adriana Kovalcik, Institute for Chemistry and Technology of Materials, Graz University of

Technology, Austria

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) as a thermoplastic microbial bio-

copolyester has attracted much attention recently, because of its biodegradability, non-

toxicity and renewability. PHBV find its application mainly in the area of packaging and

medicine. This paper will present effect of 1–10 wt% of non-modified Kraft lignin and

methanol-fractionated Kraft lignin on oxygen and carbon dioxide permeabilities of PHBHV

films with thickness of about 120 mm. High-molecular weight polydisperse KL was

fractionated by the two-step successive extraction in dichloromethane and methanol.[1] The

initial extraction with dichloromethane eliminated low-molecular weight admixtures from

Kraft lignin and such increased its interfacial compatibility with PHBHV. The morphology of

PHBHV/lignin was studied by scanning electron microscopy and it can be stated that

PHBHV films with methanol fractionated lignin show a good distribution of lignin particles

in PHBHV matrix in difference to non-modified Kraft lignin. The obtained gas permeability

results showed that methanol Kraft lignin already in the concentration of 1 wt% decreased

permeability of PHBHV films for O2 and CO2 by about 77 and 91%, respectively.[2] The

improved oxygen and carbon dioxide barrier performance of PHBHV/lignin films can be

related to the rigid nature of lignin particles, combined with the homogeneous dispersion of

methanol Kraft lignin. Moreover, it was find that methanol-fractionated lignin increased

thermo-mechanical-oxidative stability of PHBHV films in oxygen atmosphere.

A. Gregorova, V. Sedlarik, Desalination and Water Treatment 2015, accepted, DOI:

10.1080/19443994.2015.1036364.

A. Kovalcik, M. Machovsky, Z. Kozakova, M. Koller, React. Funct. Polym. 2015, 94, 25.

42

L27

Sustainable and environmentally friendly allylation of organosolv lignin

Lena Charlotte Over, Michael A. R. Meier? Karlsruhe Institute of Technology (KIT),

Germany

Lignin is one of the most abundant biopolymers on earth, third only after cellulose and

chitin.[1] Thus it is a highly available renewable resource. Especially for the production of

aromatic compounds, lignin probably is the most promising alternative to petroleum-based

materials. The functionalization of both the phenolic and aliphatic hydroxyl groups in lignin

is essential for material properties of the macromolecular structure for application in

polymer chemistry.[2]

The alkylation of phenols with organic carbonates was shown to be non-toxic, sustainable

and effective in the presence of under-stoichiometric quantities of 1,8-

diazabicyclo[5.4.0]undec-7-ene (DBU) and potassium carbonate.[3] This functionalization

methodology is already well-established for different phenols that can serve as model

substances for phenolic hydroxyl groups in lignin.

For organosolv lignin (OL), comparative studies of different bases and temperatures were

performed to optimize the allylation with diallyl carbonate under solvent-free conditions.

Due to a better solubility, the reactivity of OL is significantly higher towards the allylation of

both the phenolic and aliphatic hydroxyl groups using tetrabutylammonium bromide

(TBAB) as a base. Up to 90% of all lignin hydroxyl groups were thus functionalized by

allylation.[4] The allylated lignin is shown to be a reactive ene component for polymer

chemistry.

[1]R. Whetten, R. Sederoff, Plant Cell 1995, 7, 1001.

[2] S. Sen, S. Patil, D. S. Argyropoulos, Green Chem. 2015, 17, 1077.

[3] O. Kreye, L. C. Over, T. Nitsche, R. Z. Lange, M. A. R. Meier, Tetrahedron 2015, 71,

293.

[4] L. C. Over, M. A. R. Meier, Green Chem. 2015, accepted, DOI: 10.1039/c5gc01882j.

43

L28

Crossing the biomass feed-stocks for novel bio-sourced polymers

Henri Cramail, Audrey Llevot, Etienne Grau, Stéphane Carlotti, Stéphane Grelier LCPO,

University of Bordeaux, France

Petrol depletion and environmental concerns lead the chemical industry to consider

renewable resources as building blocks for the synthesis of polymers. Among the available

bioresources, vegetable oils have been intensively studied for the synthesis of biobased

polymers because of their good availability. However, due to their inherent aliphatic

structures, polymers obtained from fatty acid derivatives generally exhibit restricted

thermomechanical properties.[1] It is thus important to investigate other bio-based

molecular platforms to broaden the palette of renewable polymers.

Lignin, the second most abundant renewable polymer after cellulose, is a source of

phenolic compounds after depolymerization. In order to develop novel difunctional

aromatic synthons, phenolic substrates potentially derived from lignin were dimerized via a

“green” enzymatic process enabling the synthesis of biphenyl compounds in large quantity

and high yield. Further chemical modifications of these biphenyl dimers yielded a bio-

platform of aromatic derivatives ready for polymerization.[2] For instance, semi-aromatic

polyesters were prepared by copolymerization of biphenyl diols with various diesters

derived from fatty acids and ADMET (acyclic diene metathesis) polymerization of bis-

unsaturated biphenyl derivatives, produced by esterification of methyl vanillate dimer with

undecenol, yielded materials with good thermal stability over 300 °C.[3]

[1] L. Maisonneuve, T. Lebarbe, E. Grau, H. Cramail, Polymer Chemistry 2013, 4, 5472.

[2] A. Llevot, H. Cramail, S. Carlotti, G. Grau, S. Grelier, 2014, New process for preparing

biphenyl compounds, EP14306566.2.

[3] A. Llevot, H. Cramail, S. Carlotti, G. Grau, S. Grelier, 2014, New phenolic polymers and

preparation processes thereof, EP14306563.9.

44

L29

New fully biobased macromolecular architectures: analysis of the structure-property relationships of synthesized copolyesters from

building blocks

Thibaud R Debuissy, Eric Pollet, Luc Averous, Strasbourg University, France

Introduction: In recent years, the major enlargement of the biobased monomers library

allowed an outstanding development of fully biobased polymers. The Figure (below)

presents four renewable building blocks and the corresponding synthesized aliphatic

copolyesters such as, poly(butylene succinate-co-butylene adipate) (PBSA),

poly(propylene succinate-co-butylene succinate) (PPBS), poly(propylene adipate-co-

butylene adipate) (PPBA) and poly(propylene succinate-co-propylene adipate) (PPSA).

Although the synthesis of some of these copolyesters has been largely and previously

reported, this work reports for the first time (to the best of our knowledge) the synthesis

and full characterization of PPBA and PPSA. This study was mainly focused on the

variations of the copolyesters architectures through their corresponding compositions, and

their effects on the properties.

Results and discussions: High molar mass PPSA and PPBA have been synthesized

successfully (in bulk), via a two-stage melt polycondensation with an organometallic

catalyst. 13C NMR analysis of the copolyesters demonstrated equivalent reactivity of the

monomers to form copolymers with random distributions. Concerning the analysis of the

structure-thermal properties relationships, results showed that PPBA has higher thermal

stability compared to PPBS with an increase in the onset degradation temperature. This

study clearly highlighted considerable variations on thermal properties and crystallinities by

exchange between succinic and adipic acid, and replacement of 1,4-butanediol (BDO) by

1,3-propanediol (PDO). For example, PPBA presented amorphous or semi-crystalline

behavior depending on the PDO content and lower Tm and Tg compared to PPBS.

Besides, PPSA exhibited exclusively amorphous behavior with an important variation of

the Tg. With such a very precise control of polymers architecture, thermal properties of

these copolyesters can be modulated.

Conclusions: Innovative fully renewable macromolecular architectures (PPSA and PPBA)

based on aliphatic copolyesters were successfully synthesized and characterized.

Compared to others conventional biobased copolyesters, PPSA shows for instance a fully

amorphous behavior with a low Tg (especially at high adipic acid content). PPBA at high

PDO content (around 80%) presents also an amorphous behavior with low Tg. However at

lower PDO content, PPBA is semi-crystalline and in a solid state at room temperature for

low 1,3-propanediol content. All these properties variations in connection with the

corresponding modulated architectures could open new fields for these “green” polymers,

obtained from renewable conventional building blocks, for short term and biomedical

applications.

Claims: The research leading to these results has received funding from the European

Union Seventh Framework Programme (FP7/2007-2013) under grant agreement nº

311815.

45

L30

Composite models for compression moulded cellulose fibre-reinforced brittle thermoplastics

Nina Graupner1, Gerhard Ziegmann2, Jörg Müssig1, 1Bremen City University of Applied

Sciences, Germany, 2Institute for Materials and Plastics Processing, Clausthal University of Technology, Germany

Due to growing environmental awareness and increasing crude oil prise composites

produced from renewable and biobased resources become more and more important.

Problems of cellulose fibre-reinforced composites exist in terms of prediction and

calculation of the mechanical properties, especially regarding strength. The present study

shows an approach to calculate the tensile strength of brittle compression moulded

cellulose fibre-reinforced thermoplastic matrices (PLA and PHB) with a nearly

unidirectional fibre orientation (fibre orientation factor 0.8). For this approach regenerated

cellulose fibres (lyocell) of variable fineness (1.3, 3.3, 6.7, 12.0 and 15.0 dtex) with

different fibre loads (20, 30 and 40 wt%) as well as bast fibre bundles (hemp, kenaf and

ramie) were used as reinforcement. Some published models were applied to our

compression moulded composites. While the rule of mixtures as well as the Kelly-Tyson[1]

and Cox-Krenchel[2] model lead to a clear overestimation of the strength values, the model

according to El-Sabbagh et al.[3] which was developed for injection moulded composites

lead to a clear underestimation. A new model on the basis of the Kelly-Tyson and El-

Sabbagh et al. model was created for compression moulded cellulose fibre-reinforced

brittle composites. The new model considers the fibre orientation, the fibre length, the

interfacial shear strength as a function of the void fraction, the fibre agglomeration as a

function of the fibre load and the fibre strength in dependence on the elongation of the

matrix and the composites. Tensile strength values of all composites were calculated and

measured. Overall, 25 different composites were investigated. 11 of them show a deviation

from the measured tensile strength of < ± 5%, 11 of them between ± 5% and ± 10% and

only 3 of them have a deviation between ± 10% and 13%. The results show that the

developed model is valid for all investigated PLA and PHB based composites, and even

for composites with different fibre orientation angles (15, 30, 45 and 90°).

[1] A. Kelly, W. R. Tyson, Journal of the Mechanics and Physics of Solids 1965, 13, 329.

[2] A. EI-Sabbagh, L. Steuernagel, G. Ziegmann, Polymer Composites 2009, 30, 510.

[3] H. Krenchel 1964, Dissertation, Technical University of Denmark, Laboratory of

Structural Research, Copenhagen, DK.

46

L31

Non-isocyanate polyurethanes for greener foams and plastics

Andrew W Myers, Ivan Javni, Olivera Bilic, Kansas Polymer Research Center, US

Polyurethanes are one of the most widely applicable thermoset polymers, capable of

producing flexible and rigid foams, coatings, cast resins, and thermoplastic elastomers.

However, the isocyanate monomers that compose half or more of the final polymer pose

significant environmental health and safety risks during their manufacture, storage, and

reaction / application. Working with isocyanates requires substantial protective gear and

equipment, extensive training, and increased expenses and liability concerns beyond

material costs. Regulations in the European Union and some states in the US seek to

address the concerns over isocyanate use, and researchers have sought to create new

materials that give similar products without requiring isocyanates.

Non-isocyanate polyurethane technology has existed for some time, but the systems are

often slow (making it difficult to prepare foams), use expensive components, or require

only slightly less-toxic starting materials. The development of non-isocyanate polyurethane

formulations that give products that are competitive on performance and price would be a

significantly safer alternative. Non-isocyanate technology that uses bio-based feedstocks

would produce even “greener” materials, through the decrease in hazardous components

and the use of a renewable resource.

We have explored a variety of methods to produce non-isocyanate polyurethane foams,

coatings, and plastics. Specifically, non-isocyanate polyurethanes were synthesized from

bio-based cyclic carbonates and a range of amines. The effect of carbonate and amine

structure and reactivity on polyurethane properties was studied. Non-isocyanate

polyurethanes synthesized from cyclic carbonates and amines are interesting new

polymeric materials. An additional benefit of this technology is the utilization of carbon

dioxide, an inexpensive and environmentally friendly monomer. New polyurethanes have

different properties than those prepared by classical isocyanate route due to the presence

of hydroxyl groups in their structure.

47

L32

Biodegradable and renewable polymers: how to contribute to a sustainable future?

Carsten Sinkel, Andreas Künkel, Robert Loos, BASF, Germany

In 2050 very probably 9 billion people will live on earth, resulting in significant challenges.

Major tasks will be supply of food, the more efficient use of resources (raw materials,

energy), protecting the environment and prevention of further climate changes. Use of

renewable raw materials for monomer production offers the opportunity to improve

sustainability, esp. the carbon footprint. Important renewable monomers are lactic acid (for

PLA), 1,4-butanediol, succinic acid, mid chain dicarboxylic acids (for biodegradable

polyesters), 1,3-propanediol (for PTT) and furandicarboxylic acid (for PEF). Actually only

1st generation biorefineries (e.g. corn to glucose) are in place while 2nd generation

biorefineries (cellulose to glucose, xylose) are still in infant status. Technological progress

has been significant in the last years, but cost competitiveness to the fossil counterparts is

difficult to achieve. 1,3-propanediol and succinic acid are examples where the biobased

variants seem to be superior in costs and sustainability. ecoflex® F, the aliphatic-aromatic

BASF polyester, is made from terephthalic acid, butanediol and adipic acid. ecoflex® is the

preferred blend partner for biobased and biodegradable polymers which typically do not

exhibit good mechanics and processability for film applications by themselves (e.g. starch,

PLA). The BASF brand name for compounds of ecoflex® with PLA is ecovio®. The

exchange of monomers (e.g. by succinic acid) gives access to polyesters and compounds

with new properties. Organic waste management and mulch film in agriculture are two

application examples where biodegradable and renewable polymers add value.

Approximately 40% of the household waste is organic waste, which can be converted to

energy and to valuable compost. To enable this organic recycling, biodegradable organic

waste bags and coffee capsules have been developed. Mulch film offers the opportunity to

increase crop yield by reducing water consumption, improving microclimate and preventing

growth of weeds. Biodegradable mulch film is plowed in the soil after harvest thus reducing

the number of working steps. The prerequisite for these applications is the biodegradability

of the used polymer compounds. Polymer biodegradation commonly begins with the

(hydrolytic) breakdown of the main chain – often enzymatically catalyzed – followed by

mineralization of the resulting small molecules by microorganisms present in the

respective habitat. Therefore elucidation of the interaction of microorganisms and their

respective enzymes with polymer substrates in different environments and deducing

relevant structure-property relationships is an important task of BASF biopolymer

research. Biodegradable and renewable polymers will not resolve the will contribute to its

solution.

48

L33

Direct and efficient polymerization of levulinic acid via Ugi multicomponent reaction

Manuel Hartweg, C. Remzi Becer, Queen Mary University of London, UK

Nowadays, the utilization of sustainable chemicals is of major significance due to the

dwindling of fossil resources. Converting lignocellulosic biomass, the most abundant and

bio-renewable biomass on earth, into valuable chemicals, materials and plastics has a

great potential. Among the chemicals derived from sugar-based cellulose, levulinic acid is

a good representative, as it is cost competitive and the synthesis on industrial scale is

already achieved. In contrast to other methods, which normally require the derivatization of

levulinic acid, we here describe an direct access towards polyamides. Therefore, the Ugi

multicomponent reaction was used in a robust, fast, and efficient process in order to

manufacture polymers from levulinic acid, diisocyanids, and different diamines. The

obtained polyamides displayed good dispersities and molecular weights, whereat the latter

can be tuned depending on the chain length of the incorporated diamine, resulting in

polyamides with distinct glass transition (52 – 120 °C) and decomposition temperatures

(377 – 462 °C).

49

L34

Tailored isohexide monomers by catalytic isomerisation & amination

Rebecca Pfützenreuter, Marcus Rose, RWTH Aachen University, Germany

Isohexides and their amine derivatives are suitable biogenic building blocks for polymers

from renewable resources. Isosorbide can be produced starting from starch as well as

from cellulosic biomass. Its isomers isomannide and isoidide can be obtained by

isomerisation yielding an equilibrium isomer mixture with the isoidide as the favoured

product. Isoidide is also the most interesting as monomer since it provides the best

accessibility of the hydroxyl groups (all-exo) and thus, yields polymers with higher

molecular weights than its isomers. However the occurrence of isoidide and its precursors

in nature is negligible. Therefore, the production via isomerisation from isosorbide is in

demand. This reaction was already published in the 1940’s using Ni catalysts and harsh

conditions (>200°C, 100 bar H2). More recently, milder reaction conditions were

described applying a commercial Ru/C catalyst. Furthermore, also the amine derivatives of

isohexides are more and more used for the synthesis of biogenic polymers. These amines

can be produced from the isohexide alcohols by amination with ammonia in solution. Thus

far, only molecular-Ru-catalysts and enzymes are reported to catalyse this reaction.

In this contribution the mildest conditions published so far for the isosorbide isomerisation

are reported and kinetic studies for a better understanding of this reaction are shown.

Concerning the amination, for the first time, the feasibility of a heterogeneously catalyzed

amination of isohexides using conventional solid catalysts is proven. An unusual effect of

stereoselectivity of the bifunctional isohexides was observed and investigated. Catalysts

were screened and reaction conditions optimised. Overall, this work poses a foundation for

the future development of commercial processes for the production of isohexide-based

monomers.

50

L35

Influence of biopolymers on the recycling of conventional plastics

Blanca M. Lekube, Christoph Burgstaller, Transfercenter für Kunststofftechnik GmbH

Biodegradable materials have introduced themselves in many market segments such as

packaging or short life products as a real alternative to conventional plastics and Polylactic

acid (PLA) is one of the most widespread materials amongst them. PLA replaces specially

polyethylene terephthalate (PET) and polystyrene (PS) for films and packaging

applications and since the separate collection of the biopolymer has not yet been

established, its potential risk of contaminating other plastics streams for recycling is

already of growing concern. Therefore, the aim of this work was to investigate the

miscibility and interactions of PLA/PET and PLA/PS mixtures over the entire range in order

to evaluate the effects of biopolymers on the mechanical recycling of conventional plastic

streams. To this end, the recycling process of the mixtures was simulated by means of a

co-rotating twin screw extruder and the yielded granules were, after a drying step, molded

into universal test specimen via injection molding. Characterization methods comprised

mechanical, thermal and rheological analysis as well as evaluation of the morphology by

SEM. An almost linear behavior was observed for both PET and PS for the static

properties such as elastic modulus and tensile strength due to the fine dispersion achieved

through intensive mixing in the extrusion and injection molding processes. In the case of

PET, dynamic properties such as impact strength were influenced even with small

concentrations of PLA in the blend. Rheological analysis showed a severe drop of

viscosity already at 1 wt% PLA, proving the incompatibility between the two components in

the melt since the viscosity of the blends show a negative deviation from the log-additivity

rule. Parallel-plate rheometry and DSC analyses, which showed 2 glass transition

temperatures over the entire composition range, gave prove of the immiscibility of the

mixtures as well. Both temperatures fluctuated slightly irrespective of composition, which

indicates interaction between the materials to some degree. One possible explanation

could be the occurrence of transesterification reactions. Regarding PS, dynamic properties

followed a linear behavior, but melt flow rate measurements showed incompatibility

between PS and PLA.

In conclusion we found that recycling is possible but only for specific applications, since

the dispersion achieved in the processing of the blends is fine enough to reach good static

properties, however not for dynamic properties. Furthermore, rheological and thermal

analysis indicates incompatibility and immiscibility of the mixtures. Although some

interactions were observed, these were too low to have effects on the dynamic or flow

properties of the blends. Further works should focus on the improvement of the miscibility

between PLA and the polymers to improve blend properties.

51

L36

Replacing styrene in thermoset polyesters

Stuart R Coles1, Jeffrey P Youngblood2, Andrew B Sellars1, Andrew J Clark1, 1University of Warwick, UK, 2Purdue University, US

Composites offer high strength and stiffness at a lower density compared to other

structural materials, therefore are of growing use to a variety of lightweight structures in

order to reduce emissions and improve performance. However, traditional composites

have the highest embodied carbon content of all engineering materials with limited

methods of recycling. Therefore moving composites to a biobased sourcing can have a

large impact in the eco-footprint of these materials.

In this work bio-derived analogues of styrene (“bio-styrenes”) were used as reactive

thinners in thermoset polyester formulations and compared to the base resin. Gel points of

formulations including a methoxy-based derivative are reached faster due to the electron

donating effect of the methoxy group; this presents issues with the manufacturing of

polyesters when completely replacing styrene with the bio-styrene analogue. Water uptake

was not affected by the bio-derived substitution, whereas glass transition temperature

varied ±5 °C depending on the substituent. Reactive diluent blends of biostyrenes with

styrene of up to 50% showed no statistical difference with pure styrene in both tensile

strength and modulus and so may be a viable styrene replacement in polyester used for

fibreglass.

52

L37

Biopolymers to make emulsions and using them as injectable scaffolds

Shengzhong Zhou1, Bernice Oh1, Alexander Bismarck2 Polymer & Composite Engineering (PaCE) Group,

1 Department of Chemical Engineering, Imperial College London, UK and 2 Institute of Materials Chemistry and Research, Faculty of Chemistry, University of Vienna, Austria and

Emulsion templating has emerged as effective method to synthesise macroporous

polymers with tailored pore morphology and physical properties. High or Medium Internal

Phase Emulsions (HIPEs or MIPEs) with a continuous phase consisting of or containing

monomers are used as templates for the preparation of very high porosity macroporous

polymers, called poly(merized)M/HIPEs. However, this method typically requires the use of

large amounts of surfactants or particulate emulsifiers to stabilize immiscible liquid phases

and monomers and a crosslinker in the continuous minority phase to “solidify” the

template, which may not be desirable for biomedical applications. We will show that

polyHIPEs with porosity greater than 75% can be produced from inverse (oil-in-water)

HIPEs solely stabilised using suitably modified biopolymers. The biopolymer was modified

by further grafting thermoresponsive polymers. The resulting copolymer acts

simultaneously as emulsifier and thermoresponsive gelator and forms upon removal of the

templating oil phase and water the bulk of the resulting polyHIPE. As can be expected, the

resulting polyHIPEs are also thermoresponsive and injectable hydrogels, which remain

intact when immersed into water at physiological temperature but do dissolve below their

lower critical solution temperature. We will also demonstrate that cells grow into the

scaffold and that this scaffold can be extruded through a needle, with no damage to the

cells.

53

Abstracts

Part 2: Posters

54

P1

Evaluation of environmental degradability of poly(butylene n-alkylene dicarboxylate)s

Takuro Baba, Yuya Tachibana, Shota Suda, Ken-ichi Kasuya, University of Gunma, Japan

Although aliphatic polyester was generally assumed as an environmental biodegradable

polymer, the biodegradability of all polyesters had not been evaluated. In this presentation,

we evaluated the biodegradability of poly(butylene n-alkylenedicarboxylate) (PBAD)s

depended on the number of methylene unit (n). Nine PBADs were obtained by the direct

polycondensation with 1,4-butanediol and several alkylenedicarboxylic acids in which n is

2 to 10. Biodegradability of PBADs was evaluated using biochemical oxygen demand

(BOD) method, clear zone method, and identification of isolates. Although, all monomers

were degraded rapidly, eight PBADs had biodegradability and one PBAD consisting of 1,4-

butanediol and dodecanedioic acid (n = 10) did not show the BOD-biodegradability. The

environmental distribution of PBADs-degrading microorganism evaluated by clear zone

method indicates even-odd effect based on n. In addition, 108 microorganisms, which

degraded PBADs, were isolated from Japanese soil and 31 strains were genetically

identified.

55

P2

Extraction of betula pendula with an ionic liquid

Veronika Strehmel1, David Strunk1, Nadine Strehmel2, 1Niederrhein University, Germany, 2Leibniz Institute of Plant Biochemistry, Germany

Silver birch (Betula pendula) has been a widespread tree species in northern Europe

comprising about 25 % lignin.[1,2] Furthermore, an incredible amount of waste wood arises

every year. Recycling and processing of wood require selection of efficient solvents.

Ionic liquids have gained a remarkable interest in processing of renewable raw materials

due to their high thermal stability and their negligible vapor pressure.[3] Among the ionic

liquids, 1-butyl-3-methylimidazolium chloride has received increased interest because it is

easy to manufacture and exhibits better dissolution properties in comparison with

traditional organic solvents.

Extraction of a rasped and sieved birch interior wood and birch bark with methanol

resulted in 2 wt-% extractives of the interior wood and 12 wt-% extractives of the bark

containing both aromatic as well as aliphatic signals in the 1H NMR spectra. The residue

was further extracted with 1-butyl-3-methylimidazolium chloride for 4 h resulting in 5 wt-%

soluble parts of birch wood and 13 wt-% of birch bark. The amount on ionic liquid soluble

constituents increased for both raw materials in the presence of AlCl3 as catalyst.

Prior to NMR and LC MS analysis, the reaction mixture was diluted with water and

extracted with ethyl acetate. 1H NMR analysis showed signals of 2-hydroxymethyl furfural,

which decreased with reaction time. UPLC/ESI-QTOF MS analysis showed several

signals corresponding to further reaction products. Some products showed a time

dependent concentration although a few products did not change in concentration. The

identified signals can be linked to a diverse set of biochemical substance classes such as

diarylheptanoids, flavonoids as well as phenylpropanoids.

[1] E. Hiltunen, T.T. Pakkanen, L. Alvila, Holzforschung 2006, 60, 519.

[2] J. Liimatainen, M. Karonen, J. Sinkkonen, M. Helander, J.-P. Salminen, Holzforschung

2012, 66, 171.

[3] P. Wasserscheid, T. Welton, Ionic Liquids in Synthesis, Wiley-VCH Verlag GmbH & Co.

KGaA, Weinheim 2003.

56

P3

Cyclic organic carbonates as oxyalkylating reagents for lignin

Isabell Kühnel, Bodo Saake, Ralph Lehnen, University of Hamburg, Germany

This work presents an efficient, non-toxic and solvent-free procedure for the oxyalkylation

of lignin using cyclic organic carbonates. The oxyalkylating reagents ethylene carbonate

(EC), propylene carbonate (PC) and glycerol carbonate (GC) are characterized by low

toxicity, good biodegradability, high solubility as well as high boiling and flash points and

low vapor pressures. Comparative studies concerning the effect of temperature, reaction

time and catalyst on oxyalkylation with EC, PC and GC was performed. The oxyalkylation

show almost completely reaction of phenolic and aliphatic hydroxyl groups with

conversions up to 91% under optimized reaction conditions. This oxyalkylation procedure

allows the preparation of lignin polyols with extended carbon skeleton and exclusively

aliphatic hydroxyl groups applicable as bio-based precursor for polyurethane and polyester

synthesis.

57

P4

Synthesis of modified polycaprolactams based on renewable resources[1]

Stefan Oelmann, Michael A. R. Meier, KIT, Germany

Polycaprolactam is a polyamide with specific properties mainly used as a synthetic fiber

marketed under the trade name Perlon®. These polyamides are produced on an industrial

million tons scale at high temperatures (240 °C) utilizing petroleum base chemicals.

Current research endeavors to replace petroleum based feedstocks with renewable

materials and furthermore to achieve polymerization at lower temperatures.[2]

This work evaluates the ability to produce polyamides from renewable monomers at lower

temperatures (150 °C). Caprolactam monomers were modified to obtain novel polyamides

with tuneable properties.

By using polyunsaturated fatty acid methyl ester mixtures, it is possible to obtain the

diesters to create AA-type-monomers. 1,4-cyclohexadiene is obtained as a byproduct due

to intramolecular self-metathesis of linolenic acid derivatives.[3] In a sustainable three step

synthesis, the 1,4-cyclohexadiene can be further converted to 2-cyclohex-1-enone.[4,5]

Starting from 2-cyclohex-1-enone, a Thia-Michael-Addition and three additional steps are

used to synthesize modified monomer derivatives. The monomer synthesis is further

optimized in order to achieve high yields utilizing environmentally benign synthesis

procedures. Of particular importance is the use of less toxic reagents and the minimization

of chemical waste in order to meet the requirements of environmentally friendlier

chemistry. Via coordination-insertion ring-opening polymerization with a tin(II)2-

ethylhexanoat (Sn(Oct)2) catalyst, it is possible to create common, high molecular weight

polyamides.

[1] S. Oelmann, M. A. R. Meier, Macromol. Chem. Phys. 2015 accepted, DOI:

10.1002/macp.201500257.

[2] C. E. Carraher, J. Chem. Ed. 1978, 55, 51.

[3] H. Mutlu, R. Hofsäß, R. E. Montenegro, M. A. R. Meier, RSC Adv. 2013, 3, 4927.

[4] J. Dupont, P. A. Z. Suarez, A. P. Umpierre, R. F. de Souza, J. Braz. Chem. Soc. 2000,

11, 293.

[5] L. Montero de Espinosa, J. C. Ronda, M. Galia, V. Cadiz, J. Polym. Sci., Part A: Polym.

Chem. 2008, 46, 6843.

58

P5

Consolidated bioprocessing for production of polyhydroxyalkanotes by co-culture of Sacchraophagus degradans and Bacillus cereus from

complex polysaccharides

Shailesh S. Sawant, Bipinchandra K. Salunke, Beom Soo Kim, Chungbuk National

University, South Korea

Global energy demand and environmental concerns have stimulated increasing efforts to

produce bioenergy and biofuels directly from renewable resources. The production of

petroleum alternative compounds like polyhydroxylkanotes (PHA) from abundantly

available renewable materials in nature through consolidated bioprocessing is an

innovative approach. Here we report biosynthesis of PHA in pure cultures of marine

bacterium, Saccharophagus degradans 2-40 (Sde 2-40), its contaminant, Bacillus cereus,

and a co-culture of these bacteria (Sde 2-40 and B. cereus) degrading plant and algae

derived complex polysaccharides. Sde 2-40 degraded xylan, agar, and alginate as sole

carbon source for biosynthesis of PHA. The association of Sde 2-40 with B. cereus

resulted in increased cell growth and higher PHA production than Sde 2-40 alone. This

study provides new paradigm in PHA production through consolidated bioprocessing of

complex carbon sources by pure and co-culture of microorganisms.

59

P6

Modified β-cyclodextrin obtained from Ugi five-component reactions with carbon dioxide

Rebekka Schneider, Ansgar Sehlinger, Felix Mack, Michael A. R. Meier, KIT, Germany

Modified β-cyclodextrin, a decomposition product of starch, is highly demanded in the

pharmaceutical, food and cosmetic industry.[1] Here, an easy one-pot synthesis for the

modification of β-cyclodextrin is introduced. A variation of the Ugi reaction, the Ugi five-

component reaction (Ugi-5CR), is used for this matter.[2] Whereas the Ugi four-component

reaction has already been performed with polysaccharides,[3,4] the Ugi-5CR has only

recently found its way into polymer chemistry.[5] The Ugi-5CR requires carbon dioxide and

an alcohol (e.g. β-cyclodextrin) instead of an acid component in addition to an isocyanide,

an amine and an oxo-component. Thus, not only the scaffold is based on renewable

resources, but CO2 as alternative carbon source is incorporated. Moreover, only primary

hydroxyl groups are substituted, enabling a regiospecific substitution. The modified

cyclodextrins exhibit a better thermal stability and the solubility behaviour is improved as

well.

[1] J. Szejtli, Chem. Rev. 1998, 98, 1743.[2] I. Ugi, C. Steinbrückner, Chem. Ber. 1961, 94,

2802.

[3] A. E. J. de Nooy, G. Masci, V. Crescenzi, Macromolecules 1999, 32, 1318.

[4] A. E. J. de Nooy, D. Capitani, G. Masci, V. Crescenzi, Biomacromolecules 2000, 1,

259.

[5] A. Sehlinger, R. Schneider, M. A. R. Meier, Macromol. Rapid Commun. 2014, 35, 1866.

60

P7

Biodegradable polymeric biomaterials based on aliphatic bipolyesters for medical application

Michał Kwiecień, Marek Kowalczuk, Grażyna Adamus, Polish Academy of Science, Poland

PHA are a group of biodegradable and biocompatible aliphatic polyesters which can be

produced by large number of microorganisms. However, despite some ability to control

physico-chemical properties of PHA during biosynthesis stage, not always this method

allows to obtain a material with the desired properties. That is a reason for undertaken

research focused on modification of PHA properties via chemical way, which leads to

obtain new polymeric materials based on PHA.

The presented work is focused on elaboration of new biodegradable and biocompatible

polymeric materials containing structural segments derived from PHA biopolyesters for

potential medical applications.

A key aspect of this research was to develop new method of controlled degradation

process of selected PHA biopolyesters in order to obtain well-defined oligomers. The

developed controlled degradation method undergo via selective reduction of PHA with

using of LiBH4 allows to obtain respective PHA oligodiols. The properties of obtained PHA

oligodiols can be tuned by the selection of a particular starting aliphatic biopolyester, and

their average molar mass which can be controlled by the amount of lithium borohydride.

PHA oligodiols obtained via reduction of selected biopolyester were used in

polycondensation process with aliphatic diacid and their derivatives. This process allow to

obtain new polyesters containing structural fragments of selected PHA and with desired

properties which are not able to obtain via biotechnological way.

Acknowledgement: This work was supported by the Polish National Science Centre: No.

UOM-2013/11/B/ST5/02222

61

P8

Biodegradable polymeric system for controlled release of bioactive substances

Iwona Kwiecień1, Tomasz Bałakier1, Janusz Jurczak1, Iza Radecka2, Marek Kowalczuk2, Grażyna Adamus1, 1Polish Academy of Sciences, Poland, 2School of Biology, Chemistry and Forensic Science, Faculty of Science and Engineering, University of Wolverhampton,

UK

The aim of the research was to develop biodegradable polymeric systems for the release

of the biologically active species selected from the group of pesticides, for potential use in

agriculture. The first part of research was focused on the development of synthesis

methods of pesticide-oligomer conjugates in which pesticide is covalently bonded with

biodegradable polyhydroxyalkanoates (PHAs) oligomers by hydrolysable ester bond.

Biodegradable (co)oligomers containing pesticides moieties were obtained using anionic

ring-opening oligomerization and transesterification methods. Developed methods include:

(i) anionic ring-opening oligomerization of β-butyrolactone initiated by salts of selected

pesticides; (ii) anionic ring-opening (co)oligomerization of β-substituted β-lactone

containing bioactive moieties as a pendant group with β-butyrolactone in the presence of

carboxylates as initiators; (iii) "one-pot" transesterification of selected PHA biopolyester

dedicated for bioactive compounds with carboxyl or hydroxyl group; (iv) two-step method,

through cyclic PHA oligomers, dedicated for bioactive compounds with hydroxyl group.

The next step of the research will involve the development of the comprehensive synthetic

methods of graft copolymers composed of γ-PGA backbone and oligoesters pendant

groups via anionic grafting of β-substituted β-lactones on γ-PGA backbone.

Acknowledgement: This work was supported by the Polish National Science Centre:

decision No. DEC-2012/07/B/ST5/00627 and DEC-2013/11/N/ST5/01364

62

P9

Synthesis of isocyanate free urethanes with hydroxyl groups based on synthetic and renewable resources

Katrin Mathea1, Annett Halbhuber1, Arunjunai Raj Mahendran2, Uwe Müller2, Bernd Strehmel1, 1University Niederrhein, Germany, 2Wood K Plus

Epoxidized synthetic and renewable raw materials react with carbon dioxide which results

in the formation of cyclic carbonates. The latter possess the capability to react with

amines resulting in urethanes with hydroxyl groups. Different catalysts were tested to

decrease the reaction time, which takes several hours without any catalyst. These

reactions depict important alternatives compared to the conventional urethane chemistry.

Interestingly, the hydroxyl groups formed during urethane formation can promote the

adhesion on different substrates. This makes such materials interesting for coating

applications.

The reaction of different epoxides with carbon dioxide proceeds according to a pseudo-first

order kinetics. Reaction temperature was varied between 70-140°C showing that there

exists an optimum for such a complex reaction medium comprising the epoxy compound,

CO2 and the catalyst. Synthetic epoxides revealed a higher reactivity compared to those

derived from natural resources. Epoxidized linseed oil exhibited an acceptable reactivity

with CO2 and conversion on carbonate groups.

The second step, the formation of the hydroxyl comprising isocyanate free urethane,

followed a second order kinetics. The reaction between the cyclic carbonate and the amine

proceeds relatively slow. Nevertheless, catalysts such as triazabicyclodecene (TBD), and

lithium triflate (LiOTf) have significantly decreased the reaction time. Further some acidic

and basic catalysts were also investigated.

Finally, the paper discusses the properties of isocyanate free urethanes from different raw

materials for coating applications.

63

P10

Renewable high Tg polymers via a novel Biginelli polycondensation

Andreas C. Boukis, Audrey Llevot, Michael A. R. Meier, KIT, Germany

A novel and straightforward multicomponent one-pot polymerization was investigated in

this work.

The Biginelli reaction is a versatile multicomponent reaction of an aldehyde, a β-ketoester

(acetoacetate) and urea/thiourea yielding diversely substituted 3,4-dihydropyrimidin-2(1H)-

ones (DHMPs). In this study, renewable diacetoacetate monomers of different backbone

chain length (C3, C6, C10, C20), were prepared via a simple transesterification of

biobased diols and a β-keto ester. The diacetoacetate monomers were then reacted with

the renewable dialdehydes terephthaladehyde and divanaillin in a Biginelli type step

growth polymerization. The herein obtained DHMP polymers (polyDHMPs) displayed high

glass transition temperatures (Tg) up to 203 °C and molecular weights of 20 kDa and

higher. Furthermore, the Tg was tuned by variation of the dialdehyde or the diacetoacetate

component.

Keywords:

Multicomponent Reactions, Biginelli Reaction, Renewable Polymers, Step Growth

Polymerization

64

P11

Towards greener epoxy resins based on waste frying oil

Felipe C Fernandes, Kerry Kirwan, Maria Sotenko, Stuart Coles, University of Warwick,

UK

Vegetable oils are strong candidates to fulfil the need for eco-friendly resources for

different technological areas as they present low cost, renewability, availability and

reactive groups that can be explored to produce diverse compounds. Among them,

epoxidized vegetable oils play an important role as plasticizers and base for epoxy resins.

However, there are serious concerns about the use of vegetable oils for engineering

applications as a big portion of them are being extracted from crops originally cultivated for

food.

The use of waste vegetable oil for a novel oleochemistry is an attractive strategy as it

overcomes the discussion about the origin but also addresses a solution of the oil

disposal. Waste oils are serious pollutants as they can severely compromise the oxygen

levels of freshwater whilst cannot be treated by standard household wastewater

processes.

Due to frying, these oils present a complex mixture of by-products that lead to

heterogeneous physico-chemical properties. Methodologies to eliminate undesired

products from the oil have been investigated to remove highly oxidised products and

monoglycerides. Waste, neat and purified vegetable oils were epoxidized via different

methods and the purification step proved to affect positively the conversion and selectivity

of the procedure with mCPBA.

Blends of epoxidized waste vegetable oil (up to 30 wt. %) and commercial epoxy resins

were prepare and the materials produced were curable in 24 h at r.t similarly to pure resin.

After post-curing, mechanical tests revealed an increase of up to 900 % in elongation with

higher oil content suggesting its action as plasticizer.

65

P12

Determination of antioxidant activity of new biobased macrobisphenols

Armando Reano, Florent Allais, Anne-Marie Riquet, Sandra Domenek, AgroParisTech,

France

Ferulic acid, a component of lignocellulosic biomass, exhibits several interesting

physical/mechanical and biological properties (e.g., high thermal stability, antiradical and

antimicrobial activities). Present in relatively large quantities in rice and wheat bran as well

as in beetroot pulp, ferulic acid revealed itself as a valuable building block for the

development of new biobased (macro)molecules. In order to valorize it, we synthesized,

through a lipase-catalyzed reaction, a new class of ferulic acid-based macrobisphenols to

be used as functional macromolecules. This methodology involving Candida antarctica

lipase B – a well known enzyme used to perform high yielding (trans)esterifications –

allowed the efficient coupling of ethyl dihydroferulate (obtained from ferulic acid) with

biobased polyols (i.e., 1,4-butanediol, 1,3-propanediol, glycerol and isosorbide).

Based on ferulic acid properties, we decided to focus on potential antioxidant activity in

order to use them as biobased additives in polymers matrices. Antioxidant activity was

determined in liquid and solid media, through DPPH analysis, and OIT and EPR analyses,

respectively. DPPH studies revealed remarkable antiradical activity in ethanolic media and

allowed to determine structure-activity relationships (SARs), while OIT analysis showed

significant antioxidant activity in polypropylene and poly(butylene succinate) matrices. EPR

analysis allowed to study radical stability in polymers matrix.

66

P13

Synthesis, characterization, biological properties and polymerizations of new bio-based macrobisphenols derived from ferulic acid

Armando Reano, Florent Allais, Florian Pion, Oulame Mouandhoime, Sandra Domenek, Paul-Henri Ducrot, Tiphaine Clement, AgroParisTech, France

Ferulic acid, a component of lignocellulosic biomass, exhibits several interesting

physical/mechanical and biological properties (e.g., high thermal stability, antiradical and

antimicrobial activities). Present in relatively large quantities in rice and wheat bran as well

as in beetroot pulp, ferulic acid revealed itself as a valuable synthon for the development

of new biobased (macro)molecules. In order to valorize it, we synthesized, through a

lipase-catalyzed reaction, a new class of ferulic acid-based macrobisphenols to be used as

functional macromolecules. This methodology involving Candida antarctica lipase B

allowed the efficient coupling of ethyl dihydroferulate (readily obtained from ferulic acid)

with biobased polyols (i.e., 1,4-butanediol, 1,3-propanediol, glycerol and isosorbide).[1]

Incorporating ferulic acid moieties, these macrobisphenols are expected to exhibit

antiradical and antimicrobial activities, making them potential biobased additives in

polymer matrices. To evaluate these potentialities, antiradical activity has been determined

using established DPPH procedure and OIT analyses. In addition, antimicrobial activity

was evaluated by studying the inhibition profile of the macrobisphenols against various

microorganisms (Gram positive and negative bacteria, and yeast) in liquid cultures. These

new biobased macrobisphenols have then been used as macromonomers to provide

alternating aliphatic-aromatic copolyesters[2] and polyurethanes[3] through their

polycondensation with, respectively, bio-based diacyl chlorides and commercially available

isocyanates. The Tg of these new biobased thermoplastics can be finely tailored (from 0 to

130 °C) giving access to applications requiring polymers with high as well as lower glass

transition temperatures. More recently, these macrobisphenols have been used for the

preparation, through an oxidase-mediated aryl-aryl coupling, of linear homogeneous

phenolic homo-oligomers.[4]

67

P14

Thermal properties of cellulose acetate blends with thermoplastic urethanes and plasticizers

Rafael Erdmann, Stefan Zepnik, Stephan Kabasci, Hans-Peter Heim, Fraunhofer Society,

Germany

The use of bio-based polymers in technical products or in general becomes more and

more important, due to the change in society towards more ecological thinking. Cellulose

acetate (CA) is based on its thermal and mechanical characteristics in comparison with

other bio-based polymers more suitable for long-life and durable applications.

Thermoplastic CA exhibits outstanding properties as a high transparency and good me-

chanical properties which make it comparable with petrochemical based polymers like

poly-styrene (PS) and acrylnitril-butadiene-styrol copolymer (ABS) that are manly used for

tech-nical applications. The main drawback why CA is currently not used for this kind of

use is its poor resistance against impact. Therefore, we investigated CA blending with

thermoplastic urethane (TPU) to promote toughness of the material.

The poster will show the thermal properties of the plasticized CA as well as the plasticized

CA blended with thermoplastic urethane as toughening agent. Three different eco-friendly

plasticizers (citrate and acetate based) in different concentrations were used to investigate

their influence on the thermal properties of CA. Furthermore, combinations between the

plas-ticized CA and the TPU were analyzed using differential scanning calorimetry (DSC)

and thermogravimetric analysis (TGA). The plasticizer efficiency, which is visible in a

strong decrease of the glass transition temperature Tg, is linked with the plasticizer

concentration as well as the miscibility between plasticizer type and CA.

In general, with increasing plasticizer concentration the glass transition temperature Tg of

the plasticized CA decreases constantly. This significantly improves the processibility and

simultaneously increases the processing window of CA. Plasticizers with solubility

parameters close to those of CA showed a better plastication efficiency as the other ones.

As a conse-quence, the thermal properties of CA can not only be adjusted by the amount

of plasticizer but also by using a more effective plasticizer (more compatible plasticizer) at

constant concentra-tion. A further parameter for adjusting the glass transition temperature

is the content of TPU in the blend which will also be shown.

68

P15

Synthesis of plant oil derived, long-chain polyethers via GaBr3-catalyzed reduction of fatty acid derived carboxylic acid esters

Patrick-Kurt Dannecker, Ursula Biermann, Jürgen O. Metzger, Michael A. R. Meier, KIT, Germany

Recently, a GaBr3/TMDS (1,1,3,3-tetramethyldisiloxane) system was introduced as an

efficient method for the reduction of esters of long-chain fatty acids and polyols, such as

triglycerides to the corresponding ethers.[1] While the reducing agent TMDS is used in

stochiometric amounts, GaBr3 can be used in catalytic amounts of 0.5-1 mol%. The

reaction is carried out under mild conditions without solvent giving full conversion of the

substrate.

Here, the GaBr3/TMDS system is applied to monomeric and polymeric plant oil derived

carboxylic acid esters and in combination with self-metathesis, ethenolysis and ADMET

polymerizations with the aim to obtain long-chain polyethers in a sustainable fashion.

[1] U. Biermann, J. O. Metzger, ChemSusChem. 2014, 7, 644; U. Biermann, J. O.

Metzger, Macromol. Eur. J. Lipid Sci. Technol. 2014,116, 74.

69

P16

Green chain – shattering polymers based on a self-Immolative azobenzene motif

Hatice Mutlu, Christopher Barner-Kowollik, KIT, Germany

The current drive to sustainable and environmentally responsibility in macromolecular

science requires alternative polymers with improved degradability based on renewable

source-derived materials.[1] Indeed, inherently all natural polymers are biodegradable,

arising from the fact that they are derived biosynthetically using diverse enzymes.

Likewise, biodegradability can also be induced in chemically synthesized polymers. Thus,

a way to obtain a biodegradable material is to synthesize polymers comprising a polymer

backbone in which one or more degradable units are embodied.[2,3] Therefore, we

introduce a strategy for the synthesis of renewable resource based amphiphilic ADMET

polymers which possess self-immolative degradable enzyme-triggered azobenzene unit,

thus establishing a new class of chain-shattering polymers. Upon treatment with the

enzyme and the coenzyme, the azo units were transformed into anime groups, which

triggered the sequential self-immolative process to degrade the polymer main chain. The

in-situ formed quinone methide intermediates were quenched by water molecules to form

stable and safe hydroxymethylphenol derivatives. The degradation of our system contrasts

with the conventional self-immolative polymers, which degrade from one chain end to the

other. We strongly believe that this system is a prime example of stimuli responsive

boiodegradable polymer. Future studies will investigate the applicability of new polymeric

material for single chain nanoparticle synthesis for applications in imaging[4] and delivery

systems.

[1] K. Yao, C. Tang, Macromolecules 2013, 46, 1689.

[2] M. Mitrus, A. Wojtowicz, L. Moscicki, Thermoplastic Starch, Wiley-VCH, Weinheim

2010 pp. 1-33.

[3] K. R. K. Senthil Kumar, G. Manoj varma, K. Krishna, Int. J. Pharm Sci. Rev. Res. 2012,

1, 951.

[4] J. Willenbacher, K. N. R. Wuest, J. O. Mueller, M. Kaupp, H.-A. Wagenknecht, C.

Barner-Kowollik, ACS Macro Lett. 2014, 3, 574.

70

P17

Sustainable Derivatization of Cellulose with Diallyl Carbonate

Zafer Söyler, Felix Poschen, Michael A. R. Meier, KIT, Germany

The need for alternative and renewable resources as new precursors for the production of

synthetic polymers has become ovious. The remarkable growth and demand of the bio-

based polymers is a consequence of the excessive consumption of fossil resources and

global awareness of the high pollution caused by petroleum-based products. These

considerations drive science and technology to the less risky, non-toxic biomass as a raw

material for the chemical industry.[1,2]

There is considerably increasing interest in the preparation of industrial products from

cellulose due to its high abundance, low cost, eco-friendly and non-toxic nature. However,

it has limited applications, mainly because of its inherent properties like low solubility,

viscosity and brittleness. Chemical modification of cellulose is often necessary and

achieved by modifying its free hydroxyl groups to tune the mechanical and other

properties, which opens various strategies to substitute the conventional synthetic plactics

derived from petroleum feedstock.[3] In order to achive a sustainable derivatization of

cellulose, the used reagents for the modification are also required to be non-toxic and eco-

friendly. The development of a new class of solvents, ionic liquids (ILs), enabled new

approaches for the modification of cellulose. ILs are described as ‘green’ solvents, mainly

due to their very low vapor pressures.[4] It is proposed that the use of ILs can sufficiently

interrupt the intramolecular hydrogen bonding in cellulose and thus lead to activation of the

hydroxyl groups.[5]

In our work, diallyl carbonate, which can be considered non-toxic, sustainable and efficient

reagent, is utilized for the homogeneous modification of cellulose without any catalyst in

BMIMCl/DMSO as co-solvent. Moderate degree of substititons (DS) were obtained in the

BMIMCl/DMSO system (DS >1). The method performed in this work was an important

step forward for sustainability and represents a new approach for carbohydrate

modification. The BMIMCl–DMSO mixture can be recycled and reused for further

reactions.

[1] L. Shen, E. Worrell, M. Patel, Biofuels, Bioprod. Biorefin. 2010, 4, 25.

[2] R. U. Halden, Annu. Rev. Public Health 2010, 31, 179.

[3] B. Kaur, F. Ariffin, R. Bhat, A. A. Karim, Food Hydrocolloids 2012, 26.

[4] M. Bier, S. Dietrich, Mol. Phys. 2010, 108, 1413.

[5] L. Zhang, D. Ruan, S. Gao, J. Polym. Sci., Part B: Polym. Phys. 2002, 40, 1521.

71

P18

Renewable, fluorescent and thermoresponsive: Cellulose copolymers via cellulose functionalization in ionic liquids and RAFT-polymerization

Andrea Hufendiek, Christopher Barner-Kowollik, Michael A. R. Meier, KIT, Germany

Since the discovery of ionic liquids as solvents for native cellulose, a variety of cellulose

derivatives has been synthesized in ionic liquids.[1] Here, a combination of cellulose

functionalization in solution in ionic liquids and RAFT polymerization is employed for the

synthesis of cellulose-graft-copolymers. Thermoresponsive behavior in water is imparted

to the brush-like structures by grafting of poly(N-isopropylacrylamide) side chains.[2] A

straightforward synthetic pathway comprising transesterification of cellulose, RAFT

polymerization of N-isopropylacrylamide, and nitrile imine-mediated tetrazole-ene

cycloaddition (NITEC) chemistry is introduced, which directly generates a fluorescent

moiety during the grafting-to process.[3] The intermediate cellulose derivatives, the poly(N-

isopropylacrylamide) side chains and the cellulose-graft-copolymers were characterized in

detail by nuclear magnetic resonance spectroscopy (NMR), size exclusion

chromatography (SEC), UV-Vis measurements, turbidity measurements and fluorescence

measurements.

A. H. thanks the Fond der Chemischen Industrie for funding. C.B.-K. acknowledges

continued support from the Karlsruhe Institute of Technology (KIT) via its Helmholtz

Biointerfaces program.

[1] R. P. Swatloski, S. K. Spear, J. D. Holbrey,R. D. Rogers, J. Am. Chem. Soc. 2002, 124,

4974.

[2] A. Hufendiek, V. Trouillet, M. A. R. Meier, C. Barner-Kowollik, Biomacromolecules

2014, 15, 2563.

[3] A. Hufendiek, C. Barner-Kowollik, M. A. R. Meier, Polym. Chem. 2015, 6, 2188.