The Third Thai-Japan Bioplastics and Biobased Materials ... · PDF fileDibutyl 2,5-Furandicarboxylate ... Novamont/Thantawan Industry PLC 12:30 Lunch. ... Apichai Sawisit Suranaree

The Third Thai-Japan Bioplastics andBiobased Materials Symposium

(AIST - NIA - TBIA Joint Symposium)

20-21 December 2011

Organized byNational Institute of Advanced Industrial Science and Technology (Japan)

National Innovation Agency (Public Organization) (Thailand)Thai Bioplastics Industry Association (Thailand)

Supported by[JENESYS Program 2011]

JSPS Exchange Program for East Asian Young Researchers (Japan)National Institute of Advanced Industrial Science and Technology (Japan)

National Innovation Agency (Public Organization) (Thailand)

ScopeTo create a sustainable society, biobased plastics produced from renewable resources

(biomass) and biodegradable plastics should be the critical materials in 21st century. Thepurpose of this symposium is to overview the current research activities and global tends onbioplastics (biobased and biodegradable plastics) and biobased materials and to promotethese activities in both countries. In addition researcher exchange between Thailand and Japanwill be expected.

Topics• Biobased polymers and biodegradable polymers• Production of biomass-containing materials; adhesive, composite, and resin• Conversion of biomass-related materials to monomers and polymers• Biosyntheses of polymers; in vitro and in vivo• Polymerization of biobased monomers• Functional biobased polymers• High performance bioplastics• Processing of biobased polymers; blend, molding, and spinning• Biodegradation evaluation• Application

Symposium Programme

Tuesday, December 20, 2011

9:10-9:30 Opening RemarksDr. Sei-ichi Aiba, National Institute of Advanced Industrial Science andTechnology (Japan)Dr. Supachai Lorlowhakarn, National Innovation Agency (Thailand)Dr. Pipat Weerathaworn, Thai Bioplastics Industry Association (Thailand)

9:30-10:20 Green Polymer Synthesis: Developments of Biobased Polymers byUsing Lactic Acid as Starting MaterialProf. Shiro Kobayashi, Kyoto Institute of Technology (Japan)

10:20-10:40 Refreshment10:40-11:15 R & D of Biobased Engineering Plastics

Dr. Atsuyoshi Nakayama, National Institute of Advanced IndustrialScience and Technology (Japan)

11:15-11:50 Utilization of Carbon Dioxide as Carbon Resource: Synthesis of olefinand alcoholDr. Hisanori Ando, National Institute of Advanced Industrial Scienceand Technology (Japan)

11:50-13:40 Lunch break /Poster session13:40-14:15 Saccharification of Lignocellulosic Biomass by Cellulolytic Enzymes

from Acremonium cellulolyticusDr. Hiroyuki Inoue, National Institute of Advanced Industrial Scienceand Technology (Japan)

14:15-14:50 Preparation of PBS Copolymers by using Biobased Succinic Acid andDibutyl 2,5-FurandicarboxylateDr. Akihiro Oishi, National Institute of Advanced Industrial Science andTechnology (Japan)

14:50-15:10 Refreshment/Poster session15:10-15:45 Biobased Additives for Bioplastics

Dr. Kazuhiro Taguchi, National Institute of Advanced Industrial Scienceand Technology (Japan)

15:45-16:20 Standardisation for BioplasticsDr. Masahiro Funabashi, National Institute of Advanced IndustrialScience and Technology (Japan)

16:30-16:40 Poster Award CeremonyDr. Wantanee Chongkum, National Innovation Agency (Thailand)

Wednesday, December 21, 2011

9:30-10:00 Updated Applications for Bioplastics in GlobalTakehiko Tsuchiyama, BASF Japan Ltd., Tokyo (Japan)

10:00-10:30 Applications of Green ABS (Acrylonitrile Butadiene Styrene)Suthep Kwampian, IRPC (Thailand)

10:30-10:50 Refreshment10:50-11:20 New Technology of Bioplastics and Application of PLA

Dr. Kazue Ueda, Research & Development Center, Unitika ltd. (Japan)11:20-11:50 PBS in Papercoating Application-Alternative to LDPE

Dr. Chinnawat Srirojpinyo, PTT MCC Biochem Company Limited11:50-12.30 Latest Development for Compound Bioplastics

Dr. Phietoon Trivijitkasem, Novamont/Thantawan Industry PLC12:30 Lunch

Contents

Invited Speaker Powerpoint Presentations

Overview of AISTDr. Seichi Aiba ........................................................................................................................ 7

Green Polymer Synthesis: Developments of Biobased Polymersby Using Lactic Acid as Starting MaterialProf. Shiro Kobayashi ............................................................................................................ 9

R & D of Biobased Engineering PlasticsDr. Atsuyoshi Nakayama ...................................................................................................... 19

Utilization of Carbon Dioxide as Carbon Resource:Synthesis of olefin and alcoholDr. Hisanori Ando ................................................................................................................. 35

Saccharification of Lignocellulosic Biomass by CellulolyticEnzymes from Acremonium cellulolyticusDr. Hiroyuki Inoue ................................................................................................................ 41

Biobased Additives for BioplasticsDr. Kazuhiro Taguchi ............................................................................................................ 59

Standardisation for BioplasticsDr. Masahiro Funabashi ...................................................................................................... 77

New Technology of Bioplastics and Application of PLADr. Kazue Ueda ..................................................................................................................... 95

Poster Presentation Abstracts

Session A: Upstream and Intermediate (Fermentation and Polymerization) ...................... 109

Session B: Downstream (Processing and Application) ...................................................... 135

Session C: Degradation and Standard ................................................................................ 163

Session D: General ............................................................................................................. 173

The Third Thai-Japan Bioplastics and Biobased Materials Symposium

Poster Presentations

Ref. No Title Aurthor Organization

Session A: Upstream and Intermediate (Fermentation and Polymerization)

A-1 Metabolic Engineering of Klebsiella oxytoca to Maytawadee Sangproo Suranaree University ofProduce D-(-)-Lactic Acid in Minimal Salts Medium Technology

A-2 Screening of Succinate Producing Bacteria Panwana Khunnonkwao Suranaree University offrom A Rumen Fluid Technology

A-3 Validation of Carbon and Nitrogen Sources, Apichai Sawisit Suranaree University ofpH, and Temperature for Efficient Succinate TechnologyProduction by Actinobacillus succinogenes

A-4 Enhanced Poly(3-Hydroxybutyrate) Pawut Kanjanachumpol Chulalongkorn UniversityProduction by High-Cell-Density Fed-BatchCultivation of Bacillus megaterium BA-019from Sugarcane Molasses

A-5 Bioproduction of Short-Chain-Length-co-Medium- Chitwadee Phithakrotchanakoon Mahidol UniversityChain-Length-Polyhydroxyalkanoate from CrudeGlycerol by Engineered Escherichia coli.

A-6 1,3-Propanediol (PDO) Production via Raw Anchana Pattanasupong Thailand Institute of ScientificGlycerol Fermentation for Bioplastic Sheet and Technological Research

A-7 Production of Biopolymer Pullulan from Sehanat Prasongsuk Chulalongkorn Universitya High-yielding Tropical Strain ofAureobasidium pullulans

A-8 Double Induced Mutation of Aureobasidium Tuenchai Kosakul Chulalongkorn Universitypullulans Using Gamma Irradiation and EMS

A-9 Purification of Succinic Acid from Synthetic Sebastien Molina Suranaree University ofSolutions Using Esterification Coupled with TechnologyReactive Distillation Technique

A-10 Study of the Thermal Properties of Rectangular Suppamart Ngenruangroj Kasetsart UniversityBars of Poly (lactic acid) Stereocomplexes

A-11 Linear/star-shaped Poly(L-lactide) Blends Yodthong Baimark Mahasarakham UniversitySynthesized Through Single-Step ring-OpeningPolymerization

A-12 Synthesis of Polylactide Using Parichat Piromjitpong Mahidol UniversityBis(amidinate)tin(II) Complexes

A-13 Effect of Talc Particle Size on Crystallization Paveena Prachayawasin National Metal and MaterialsBehavior of Polylactic Acid Technology Center

A-14 Multi-Branched Poly (Lactic Acid): A Novel Yupin Phuphuak Chulalongkorn UniversityApproach for Enhancing PLLA Crystallizationfrom Biobased Compounds

A-15 Synthesis of Poly(D-lactic acid) Weraporn Pivsa-Art Rajamangala University ofUsing Direct Polycondensation Process Technology Thanyaburi

A-16 Synthesis of D-Lactide and Poly(D-Lactide) Winita Punyodom Chiang Mai UniversityUsing Novel Catalyst / Initiator System

A-17 A Pilot Scale Synthesis of Poly(L-lactic acid) Sommai Pivsa-Art Rajamangala University ofUsing a Direct Polycondensation Method Technology Thanyaburi

A-18 Synthesis of TiO2 Impregnated Bacterial Nattakammala Janpetch Chulalongkorn University

Cellulose for Photocatalytic Decompositionand Antibacterial Applications

A-19 Effect of Heat Pretreatment and Acremonium Sirapan Sukontasing Kasetsart UniversityCellulolyticus Enzymes on Saccharification ofCassava Pulp

AIST - NIA Joint Symposium 5

No. Ref. No Title Aurthor Organization

A-20 Sugar Production from Rice Straw Using Combined Metinee Wasoontharawat Suranaree UniversityChemical and Biological Treatment

A-21 Application of Thermophilic Enzymes Siriporn Chaikaew Prince of Songkla Universityand Water Jet System to Cassava Pulp

A-22 Development of Biomass Conversion Process Yuka Maeno National Institute of Advancedusing Water Jet and Hyperthermophilic Cellulase Industrial Science and Technology

A-23 Chitosan Nanoscaffold Gel via Water-based Noppadol Trirong Chulalongkorn UniversityHeterogeneous System

A-24 Structural Studies on Enzymatic Reaction of Misumi Kataoka National Institute of AdvancedBacterial Copper Amine Oxidase Industrial Science and Technology

Session B: Downstream (Processing and Application)

B-1 Preparation, Characterization and Properties of Ternary Tarinee Nampitch Kasetsart UniversityBlends with Epoxidized Natural Rubber, Poly(lacticacid) and Poly(butylene adipate-co-terephthalate)

B-2 The Influence of CaCO3 on Morphology and Bawornkit Nekhamanurak Silpakorn University

Thermal Stability of PLA Extrusion Sheet

B-3 Development and Thermal Behavior of Chamaiporn Yamoum The National Center ofCarboxymethylcellulose/Poly Lactic Scid Excellence for PetroleumComposite Films

B-4 Development of Biodegradable Nanofibers Jackapon Sunthornvarabhas National Center for Geneticfrom Poly-L-lactic Acid and Starch Blend Engineering and Biotechnologyby Electrospinning

B-5 Structure and Properties of Multi-Phase Piyawan Pukpanta Mahidol UniversityPoly (lactic acid) Blends in the Presenceof Antioxidant

B-6 Synthesis of Poly(lactic acid)/Clay Composites Kulwadee Kaewprapan Chulalongkorn Universityby in situ Polycondensation

B-7 Poly(lactic acid) – Based Thermoplastic Pranee Bunkaew Prince of Songkla UniversityNatural Rubber

B-8 Preparation, Characterization and Properties of Kanyarat Suthapakti Chiang Mai UniversityBiodegradable Polymer Blends of Poly(lactic acid)and Poly(L-lactide-co-caprolactone)

B-9 Preparation of Polymer Blends between Weraporn Pivsa-Art Rajamangala University ofPoly(L-lactic acid), Poly(butylene-succinate-co- Technology Thanyaburiadipate) and Poly(butylene adipate terephthalate)for Blow Film Industrial Application

B-10 Study of In situ Crossslink Reaction of Epoxidized Wilairat Supmak National Metal and MaterialsNatural Rubber (ENR) and PLLA-g-GMA Blend Technology Centerby Moving Die Rheometer

B-11 Preparation of Polymer Blends of Poly(lactic Sommai Pivsa-Art Rajamangala University ofacid) and (Poly[(R)-3-hydroxybutyrate-co-(R)-3- Technology Thanyaburihydroxyvalerate] (PHBV) for Textile Applications

B-12 Polylactic Acid Graft Polyvinyl Acetate as Suthawan Buchatip National Metal and Materialsa Compatibilizer for Starch Blending Technology Center

B-13 Physical Properties of PLA-Nanocomposite Nantana Jiratumnukul Chulalongkorn Universityfor Packaging Applications

B-14 Development of Poly(lactic acid) Film Clarity Raksit Supthanyakul Chulalongkorn University

B-15 Poly(butylene succinate) Conjugated with Nutcha Prasertnasung Chulalongkorn UniversityChitosan: A Novel Bioplastics with Functionof Metal Complexation

B-16 Development of Enzymatic Treated Raw Granular Sirirat Thothong Mahidol UniversityStarch /PBAT Blends as Biodegradable Materials

B-17 Studies on Compatibility of Polymer Blends Sommai Pivsa-art Rajamangala University ofbetween Poly (trimethylene terephthalate) and Technology ThanyaburiPolyamide 4 Prepared by Melt Blend Technique

The Third Thai-Japan Bioplastics and Biobased Materials Symposium6

No. Ref. No Title Aurthor Organization

B-18 Effect of Cassava Starch Foam Blended with Kaisangsri, N King Mongkut’s University ofNatural Polymers on Water Resistance and Technology ThonburiMechanical Properties

B-19 Production of Carboxymethylcellulose (CMC) Suthaphat Kamthai Chiang Mai Universityfrom Bleached Bagasses Pulp

B-20 Surface Modification of Natural Rubber Latex Sakkawet Yorsaeng Chulalongkorn Universityfrom Medical Surgical Gloves using DBD PlasmaTreatment for Chitosan Coating

B-21 Preparation of Chitosan-based Microcapsules Sasiprapha Rattanadilok Kasetsart UniversityContaining Phlai oil for Multifunctional Properties Na Phuket

B-22 Formulation and Production of Cassava Roungrong Thongtan Kasetsart UniversityStarch-Based Biodegradable Material

B-23 Self-Organising Nanostructures of Poly(e-caprolactone) Supatra Wangsoub Naresuan UniversityUsing Sorbitol Derivatives

B-24 Starch/Cellulose Biocomposites Prepared by High- Saniwan Srithongkham Mahidol UniversityShear Homogenization/Compression Molding

B-25 Physical Properties and Antioxidant Activity of Wirongrong Tongdeesoontorn Mae Fah Luang UniversityCassava Starch-Carboxymethyl Cellulose FilmsIncorporated with Quercetin and TBHQ

B-26 Emulsion Copolymerization of a Poly(lactic Kiyoaki Ishimoto Kyoto Institute of Technologyacid)-methacrylate Macromonomer with anAlkyl Methacrylate

B-27 Formulation and Optimization of Heat-Moisture Rungarun Sasanatayart Mae Fah Luang UniversityTreated Rice Starch-Glycerol-Carrageenan CompositeFilm Using Response Surface Methodology

Session C: Degradation and Standard

C-1 Comparison of CO2 Emission and Energy Papondhanai The Joint Graduate School of

Consumption between Polylactic acid (PLA) Nanthachatchavankul Energy and Environmentand High Density Polyethylene (HDPE):Thailand Case Study

C-2 Organic Fertilizer from Bioplastic Compost Rochana Tangkoonboribun Thailand Institute of Scientificand Technological Research

C-3 Compostability Studies of PLA and PLA/Starch Yosita Rudeekit National Metal and MaterialsBlends According to ISO 17088 Technology Center

C-4 Preliminary Poly lactic acid Disintegration Anchana Pattanasupong Thailand Institute of Scientificand Toxicity Testing and Technological Research

C-5 Life Cycle Environmental Impact Assessment Pomthong Malakul National Metal and Materials of Polylactic Acid Production from Cassava Na Ayudhaya Technology Center

C-6 System Development and Preliminary Walaiporn Timbuntam Kasetsart UniversityBiodegradable Evaluation Tests forBioplastic Industry by ISO 14855-2

C-7 Study of the Disintegration Behavior Pongsak Siriyota National Metal and Materialsof Polymers Starch Blend Technology Center

C-8 Determination of the Aerobic Biodegradability Parichat Intaruksa National Metal and Materialsof the Starch Based Biodegradable Plastics Technology Centerunder Controlled Composting Conditions

Session D: General

D-1 Stimulation of Advanced Technology Research and Assoc.Prof. Klanarong Sriroth Kasetsart UniversityDevelopment for Thailand Bioplastics Community

Invited Speaker

Overview of AIST

Dr. Sei-ichi AibaNational Institute of Advanced

Industrial Science and Technology (AIST)


Overview of AIST

Dr. Sei-ichi AibaSenior Researcher, Bioproduction Research Institute,National Institute of Advanced Industrial Science and Technology (AIST)AIST Tsukuba Central 6, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8566, JAPANE-mail: [email protected]

Sei-ichi Aiba obtained his Bachelor Degree, MasterDegree and Ph.D. from Tokyo University ofAgriculture and Technology, Department of IndustrialChemistry. He started his profession at the Agency ofIndustrial Science and Technology from 1978.Since2001 to present, He has been working forNational Institute of Advanced Industrial Science and

Technology (AIST) as the Research Chemist in various divisions. He was thePresident of the Japanese Society for Chitin and Chitosan from 2009 to 2010.His current research focuses on chitin, chitosan, biobased polymers.

On behalf of the organizing committee of the Third Thai-Japan Bioplastics and BiobasedMaterials Symposium, I would like to be allowed to give a brief address.

In 2009 and 2010, National Innovation Agency (NIA) and National Institute ofAdvanced Industrial Science and Technology (AIST) organized the first and secondThai-Japan Bioplastics and Biobased Materials Symposium with the support of NIA, JapanSociety for the Promotion of Science (JSPS), and AIST. The advanced progresses on Bioplasticsand Biobased Materials such as poly-lactic acid, poly-hydroxyalkanoates, biobasedpolypropylene, saccharification of lignocellulose, and standards for the evaluation of theirbiodegradability and biomass content, etc were discussed between Japanese speakers andThai participants. Many Thai researchers presented their posters, too. Thai researchers,engineers, and businessmen had much attention in this field. We had good interactions.

This year the symposium is financially supported by two Thai institutions: NIA andThai bioplastics Industry Association (TBIA). And AIST and JSPS support too.

I would like to end this word of welcome with an earnest prayer for the great successof this symposium. I sincerely hope that the symposium will reap fruitful results. And last but notthe least, we would like to extend our gratitude and thanks to all the staffs of NIA who havebeen working hard to make this symposium a successful one.

Invited Speaker

Green Polymer Synthesis: Developments of BiobasedPolymers by Using Lactic Acid as Starting Material

Dr. Shiro KobayashiKyoto Institute of Technology


Green Polymer Synthesis: Developments of BiobasedPolymers by Using Lactic Acid as Starting Material

Dr. Shiro KobayashiDistinguished Professor, Center for Nanomaterials and Devices,Kyoto Institute of Technology, Sakyo-ku, Kyoto 606-8585, JAPANE-mail: [email protected]

Shiro Kobayashi studied organic chemistry andpolymer chemistry in Kyoto University. He stayed atCase Western Reserve University as a postdoc andalso stayed at Mainz University as a Humboldt fellow.He joined Kyoto University as a staff and restartedpolymer synthesis studies. Then, he was appointed asa full professor of Tohoku University in 1986. He

moved to Kyoto University in 1997 and officially retired in 2005 to become aprofessor emeritus. Since then, he is a distinguished professor at KyotoInstitute of Technology. His research interests include polymer synthesis,enzymatic polymerizations, organic reactions, and materials chemistry. Hereceived the Award of the Chemical Society of Japan for Young Chemists(1976), the Award of the Society of Polymer Science Japan (1987), theHumboldt Research Award (1999), the Chemical Society of Japan Award(2001), the John Stauffer Distinguished Lecture Award (2002), the Medalwith Purple Ribbon (2007), and others. He is a foreign member of the NorthrhineWestfalian (German) Academy of Science since 1999. He currently serves asa member of (executive) advisory board and editorial (advisory) board forfourteen international journals.

The presentation concerns green polymer synthesis using lactic acid (LA) as a startingmaterial, where a macromonomer method was applied for the preparation of PLA-graftcopolymer. The reason of designing the graft copolymer is as follows; PLA chains aresusceptible to hydrolysis, and therefore, the property damage due to the hydrolysis of PLAchains is less when PLA chains are present as side-chain in the graft copolymer than when theyas PLA main-chain. Thus, the first example of poly(alkyl methacrylate-graft-lactic acid)(PRMA-g-PLA) in (mini)emulsion system was developed. the present polymeric materials arein a context of biomass plastics, since “biomass plastics” denote the plastics containing thebiomass content higher than 25 wt%.

In rerating to conducting green polymer chemistry, lipase- and protease-catalyzedoligomerizations of alkyl lactates will be mentioned. A new lipase (Novozym 435)-catalyzedcondensation oligomerization of alkyl lactate (RLa) monomers produced LA oligomersranging from dimer to heptamer in good to high yields. The reaction is perfectly enantioselective;only an alkyl D-lactate (RDLa) monomer produced the oligomers. On the other hand,protease-catalyzed oligomerization of RLa monomers proceeded in an L-enantioselectivemanner, giving LA oligomers ranging from dimer to pentamer in good to low yields. A novelenzymatic mechanism has been proposed.








Invited Speaker

R & D of Biobased Engineering Plastics

Dr. Atsuyoshi NakayamaNational Institute of Advanced



R & D of Biobased Engineering Plastics

Dr. Atsuyoshi NakayamaGroup Leader of Bio-based Polymers Research Group,Research Institute for Ubiquitous Energy Devices,National Institute of Advanced Industrial Science and Technology (AIST)1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan E-mail: [email protected]

Atsuyoshi Nakayama obtained his Bachelor Degree,Master Degree and Ph.D. from Osaka University,Faculty of Engineering. He started his profession atOsaka National Research Institute (ONRI) from 1988.Since 2001 to present, he has been working forNational Institute of Advanced Industrial Science andTechnology (AIST) as the Research Chemist inbiobased polymers research field.

One of the key technologies needed to create a sustainable society is biomassutilization. Typical biobased polymers are poly(L-lactic acid) and polyesters of succinic acidwith diols. However, these polymers are mainly utilized as packaging materials, that is,conventional polymers. On the contrary, engineering plastics are high performance andhigh-valued polymers. Aromatic polymers show strong mechanical properties and high meltingtemperature. Poly(trimethylene terephthalate) is a famous biobased polyesters commercializedand 1,3-propane diol can be synthesized from glucose or glycerin. Some ethylene glycol forPET is also synthesized from biomass. p-coumaric acid is an important precursor forbiosynthesis of lignin, and the utilization is studied. Polyamides are also important engineeringplastics and recent years, several chemical companies have introduced a series of biobasedpolyamides such as PA610, PA1010, PA410 and PA11. The biomass as the starting materialis a recinoleic acid in castor oil, therefore those polymers have a long methylene chain. Wehave been studying development of another type of polyamides, polyamide 4 (PA4) which canbe easily synthesized from biomass by way of L-glutamic acid, γ-aminobutyric acid andγ-butyrolactam. PA4 has a higher melting temperature and excellent tensile strengths than thoseof PA6 because of its short repeating unit. However, it is rather brittle and an elongation atbreak is 10-30%. The most characteristic property is biodegradability. PA4 is biodegraded inactivated sludge, in soil and in sea water. PA4 degrading bacterium (Pseudomonas sp.ND-11) was isolated from activated sludge. ND-11 completely degraded the polyamide in 2weeks. With the ND-11 enzyme, γ−aminobutyric acid can be recovered by hydrolysis, andγ butyrolactam also can be recovered by thermal decomposition of the polymer (chemicallyrecyclable).














Invited Speaker

Utilization of Carbon Dioxide as Carbon Resource:Synthesis of Alcohol and Alkene

Dr. Hisanori AndoNational Institute of Advanced



Utilization of Carbon Dioxide as Carbon Resource:Synthesis of Alcohol and Alkene

Dr. Hisanori AndoSenior Researcher, Research Institute for Ubiquitous Energy Devices,National Institute of Advanced Industrial Science and Technology (AIST)1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, JAPANE-mail: [email protected]

Hisanori Ando obtained his B.S. and M.S. degrees inchemistry from Shimane University and received hisPh.D. degree in applied chemistry from OsakaUniversity with the doctoral thesis “Studies oncatalytic hydrogenation of carbon dioxide intohydrocarbons”. He started his profession at the Agencyof Industrial Science and Technology in 1992. He has

been working for AIST since 2001 as a research chemist. During2003-2004, he stayed in Australia as a visiting scientist at the University ofSydney. He is a member of the committee of the Society of Synthetic OrganicChemistry, Japan-Kansai branch. His current research interest is focused onthe modification of polylactic acid.

Since carbon dioxide (CO2) is the final oxidation product of organic compounds, thelarge amount of additional energy is necessary for the transformation of CO2. Consequently,most of scientists considered that the catalytic hydrogenation of CO2 makes nonsense if thefinal aim of the research is to lower the concentration of CO2 in the atmosphere.

On the other hand, all living things utilize CO2 as an ultimate carbon resource. Fossilfuels are thought to be the fruits originated from the assimilation of CO2 by plants. From theseview points, the artificial utilization of CO2 as carbon resource must be a quite interesting andimportant subject.

I’ll introduce the effective conversion of CO2 into alcohols and alkenes by chemicalprocess with catalyst.

I would like to express my sincere acknowledgements to the organizing committee ofthe Third Thai-Japan Bioplastics and Biobased Materials Symposium for giving me a chanceto make a presentation.





Invited Speaker

Saccharification of Lignocellulosic Biomass by CellulolyticEnzymes from Acremonium cellulolyticus

Dr. Hiroyuki InoueNational Institute of Advanced



Saccharification of Lignocellulosic Biomass by CellulolyticEnzymes from Acremonium cellulolyticus

Dr. Hiroyuki InoueResearch Scientist, Biomass Technology Research Center,National Institute of Advanced Industrial Science and Technology (AIST)AIST Chugoku 3-11-32, Kagamiyama, Higashi-Hiroshima, Hiroshima 739-0046, JAPANE-mail: [email protected]

Hiroyuki Inoue received his Master and DoctoralDegree in Enzyme Engineering from graduate schoolof Natural Science and Technology, OkayamaUniversity. After his doctoral graduation, he started hisprofession at the Institute for Marine Resources andEnvironment, National Institute of Advanced IndustrialScience and Technology (AIST). Since 2005 to

present, he has been working at the Biomass Technology Research Center,AIST. During 2009-2010, Hiroyuki stayed in USA as a visiting scientist atNational Renewable Energy Laboratory, U. S. Department of Energy. Hiscurrent research focuses on the development of carbohydrate-degradingenzymes, filamentous fungi and yeast for biomass conversion.

Lignocellulosic biomass, primary composed of cellulose and hemicellulose, is anattractive source for bio-based production of chemicals and fuel generations. Cellulolyticenzymes from filamentous fungi are widely employed for breaking down cellulose andhemicellulose component into fermentable sugars. Here we present the development ofcellulolytic system from Acremonium cellulolyticus CF-2612, which is one of severalpromising cellulase-producing fungal strains for biomass hydrolysis.

Enzymatic digestibility of various pretreated biomass (softwood, hardwood, andagricultural residues) and cellulase productivity of CF-2612 was evaluated. The results showedthat hemicellulase activity in CF-2612 cellulolytic system was insufficient to degradehemicellulose component in biomass. Five cellulolytic enzymes (two cellobiohydrolases, twoendoglucanases, and xylanase) and β-glucosidase were purified and evaluated for theirsynergism degradation of pretreated biomass. The synergism differed depending on thestructure of cellulosic substrate in the pretreated biomass, suggesting the importance of enzymecomposition for the efficient hydrolysis of biomass. Compositional evaluation of the cellulolyticsystem using pretreated biomass will give a direction to develop the fungal strain producingcellulolytic enzymes optimized for hydrolysis of target biomass.
















Invited Speaker

Biobased Additives for Bioplastics

Dr. Kazuhiro TaguchiNational Institute of Advanced


















Invited Speaker

Standardisation for Bioplastics

Dr. Masahiro FunabashiNational Institute of Advanced


















Invited Speaker

New Technology of Bioplasticsand Application of PLA

Dr. Kazue UedaUnitika Ltd.


New Technology of Bioplastics and Application of PLA

Kazue UedaSenior Manager, Research & Development Center Unitika ltd.23, Kozakura, Uji-shi, Kyoto 611-0021, JAPANE-mail: [email protected]

Education: graduate Kobe University in 1986.Doctor of Engineering Kobe University in 1999.Job history: 1989 Research & Development Center,Unitika ltd.Research interests: Biodegradable plastics, PLA,PLA foams, PLA-nanocompositesSociety activities: A member of the committee of the

research group of Ecological Materials in the Society of Polymer Science, Japan.

In recent years, a spreading awareness of the need to achieve sustainable developmentand environmental preservation has prompted companies to use eco-friendly materials, suchas bio-based polymers. Demand for PLA, one of the most commercially successful bio-basedpolymers in the world, is increasing worldwide. In this keynote speech, examples ofcommercialized products of PLA in Unitika will be explained at first. Then, future challengesfor PLA moldings and foams to get higher heat resistance will be discussed from the aspect ofprocessing technology.












Session: A

Upstream and Intermediate(Fermentation and Polymerization)

Poster Presentation


A-1

Metabolic Engineering of Klebsiella oxytoca to ProduceD-(-)-Lactic Acid in Minimal Salts Medium

Maytawadee Sangproo, Pattharasedthi Pholyiam and Kaemwich Jantama*School of Biotechnology, Institute of Agricultural Technology, Suranaree University of Technology,Muang District, Nakhon Ratchaseema 30000*Corresponding author: [email protected]

D-(-)-lactic acid is used in petroleum-based plastic, textiles, medical implants anddrug carriers. Many microorganisms that produced D-(-)- lactic acid are required complexnutrients for growth. A metabolically engineered Klebsiella oxytoca was constructedto produce D-(-)-lactic acid in minimal salt medium under anaerobic conditions. To eliminateby-product formation, genes including adhE (alcohol dehydrogenase E), pta(phosphotransacetylase), and ackA (acetate kinase A) that are responsible for the mixedacid fermentation pathways were deleted. The resulted strain KMS004 produced lacticacid concentration of 38 g L-1 in which a yield of 0.85 g g-1 and maximum productivity of 0.41g/L/h were observed. In contrast, the wild type strain produced lower lactic acid at theconcentration of 6.10 g L-1. The results suggested that inactivation of adhE, ackA and ptagenes led to a significantly improved lactic acid production in KMS004. Therefore, KMS004would be a potential strain for D-(-)-Lactic acid production.

Keyword: D-(-)-lactic acid, Metabolic engineering, Klebsiella oxytoca, Anaerobic conditions,Batch fermentation


A-2

Screening of Succinate Producing Bacteriafrom A Rumen Fluid

Panwana Khunnonkwao1, Sirima Suwannakut-Jantama2 , Sunthorn Kanchanatawee1

and Kaemwich Jantama1*

1 School of Biotechnology, Institute of Agricultural Technology, Suranaree University of Technology,Muang District, Nakhon Ratchaseema 30000

2 Faculty of Pharmaceutical Sciences, Ubon Ratchathani University, Warinchamrab District,Ubon Ratchathani 34190

*Corresponding author: [email protected]

In this study, isolation of succinate-producing bacteria from a rumen fluid was carriedout under anaerobic conditions by using a modified selective medium containing monensin,crystal violet, and sheep blood. A total number of 200 bacterial isolates were preliminaryobtained under anaerobic cultivation. All isolates were initially screened for succinic acidproduction in Brain Heart Infusion (BHI) medium containing 2 g/L glucose and carbonate saltsin anaerobic serum bottles. The fermentation products were analyzed by HPLC. The resultshowed that one of bacterial isolates was found to produce succinic acid as a majorfermentative product at a concentration of 0.5 g/L. The strain was further subjected tophysiological and biochemical characterizations. This bacterium is facultative anaerobic,gram-negative, rod-shaped, non-motile, non-spore-forming, mesophilic and capnophilic.The strain exhibited positive results in oxidase, β-glucosidase, β-galactosidase and nitratereduction, but showed negative results for catalase, tryptophane (indole production),Voges-Proskauer (acetoin production), arginine dihydrolase, urease and gelatin hydrolysis.Under anaerobic conditions, the strain could ferment glucose without gas production.The strain grows at 35-39oC with a pH range of 6.0-7.5. Without CO

2 addition, the strain

produced succinate, lactate, formate and acetate at a constant ratio of 1:1:1:1. This strain iscurrently investigated for its nomenclature.

Keywords: Succinate-producing bacterium, succinate, anaerobic conditions


A-3

Validation of Carbon and Nitrogen Sources, pH,and Temperature for Efficient Succinate Production

by Actinobacillus succinogenes

Apichai Sawisit1, Chan Sitha1, Sunthorn Kanchanatawee1, Sirima Suvarnakuta-Jantama2

and Kaemwich Jantama1*1 School of Biotechnology, Institute of Agricultural Technology, Suranaree University of Technology,

Nakhon Ratchasima 300002 Division of Biopharmacy, Faculty of Pharmaceutical Sciences, Ubon Ratchathani University,

Ubon Ratchathani, 34190*Corresponding author: [email protected]

Succinate as a potential building-block chemical is currently produced by thehydrogenation of petroleum-derived maleic anhydride. However, the increase in price of oiland petroleum derivatives has made the microbial production of succinate from cheap carbonsubstrates an economically attractive option for succinate as a renewable commoditychemical. To optimize carbon and nitrogen sources for the succinate production, A.succinogenes 130ZT was cultured in medium containing different sugars and nitrogen sourcesunder anaerobic batch fermentation in small anaerobic bottles. Succinate at concentration of6.2 g/L was produced from 10 g/L glucose or lactose in the medium containing 5 g/L yeastextract at 24 hours. Batch fermentation by Actinobacillus succinogenes 130ZT with an initialglucose concentration of 10 g/L were also investigated in 100-mL anaerobic bottles to studyfermentation parameters affecting the succinate production including types and concentrationsof nitrogen and sources, initial pH of the growth medium (pH 4.5-9.0) and temperature(25-45oC) were studied. The results indicated that A. succinogenes 130ZT was able tofermented glucose to the major products, succinate, acetate and formate. While, ethanol and2,3 propanediol were formed as minor fermentation products. According to the variousnitrogen sources investigation, it revealed that yeast extract was found to be the best nitrogensource in succinate production by this A. succinogenes 130ZT, but its price was too high.However, succinate concentration at 6.22 g/L was produced from 10 g/L glucosesupplemented with 5 g/L spent brewer’s yeast extract which was comparable to that obtainedin fermentation using commercial yeast extract (6.37g/L). This suggested that spent brewer’syeast extract could be an alternative source of nitrogen for the economical succinateproduction. Based on these results, the cost effectiveness of succinate production could beobtained from glucose or lactose fermentation supplemented with the spent brewery yeast.In term of the optimized pH and temperature evaluation, the optimized initial pH at 8.0 andtemperature at 37oC resulted in 6.3 g/L succinate formation with a yield of 68.73%. Theseresults obtained from this study may facilitate in designing a better strategy for the productionof succinate by A. succinogenes 130ZT.

Keywords: Succinic acid, Actinobacillus succinogenes, bath fermentation


A-4

Enhanced Poly(3-Hydroxybutyrate) Productionby High-Cell-Density Fed-Batch Cultivation of

Bacillus megaterium BA-019 from Sugarcane Molasses

Pawut Kanjanachumpol1, Nuttha Thongchul2, Songsri Kulpreecha1

1 Department of Microbiology, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand.2 Institute of Biotechnology and Genetic Engineering, Chulalongkorn University, Bangkok 10330, Thailand

Poly(3-hydroxybutyrate) [P(3HB)] production was operated in 10-L fermentor undercontrolled pH, temperature, agitation speed and aeration rate. It was observed that highproduction rate and yield of P(3HB) could be achieved from high cell density of B. megateriumBA-019 cultivated in the simple medium containing molasses. Among 4 initial concentrationsof molasses present in the medium, 60 g/L total sugars initially present in the molasses mediumgave the maximum cell growth (32.48 g/L) and P(3HB) production (8.75 g/L) at 12 h with thecorresponding specific growth rate of 0.23 h-1, biomass yield to substrate (Y

x/s) of 0.66, P(3HB)

yield to substrate (YP(3HB)/s

) of 0.19, and P(3HB) yield to cell (YP(3HB)/x

) of 0.28 in batchcultivation. Further increasing cell and P(3HB) production were accomplished in fed-batchcultivation. The effects of C/N ratios (5:1, 10:1, 12.5:1, 15:1 and 20:1 in feeding solution)on cell and P(3HB) production were investigated during fed-batch fermentation. Usingexponential feeding, the optimal feeding medium with the C/N ratio of 12.5:1 gave maximumcell concentration of 72.45 g/L and P(3HB) concentration of 32.77 g/L at 21 h cultivation withthe increasing P(3HB) productivity of 1.56 g/L×h as compared to 0.73 g/L×h obtained frombatch culture.

References:1. A.O.A.C. 1975. Official Methods of analysis. The Association of Official Analytical Chemists, 12th ed.,

Horwits, Washington, USA. pp. 1015.2. Bengtsson, S., Pisco, A.R., Reis, M.A.M. and Lemos, P.C. 2010. Production of polyhydroxyalkanoates

from fermented sugarcane molasses by a mixed culture enriched in glycogen accumulating organisms.Journal of Biotechnology. 145: 253-263.

3. Bernfeld, P. 1995. Amylase, alpha and beta. Methods in Enzymology. 1: 149.4. Comeau, Y., Hall, K.J. and Oldham, W.K. 1988. Determination of poly-3-hydroxybutyrate and poly-

3-hydroxyvalerate in activated sludge by gas-liquid chromatography. Applied and EnvironmentalMicrobiology. 54: 2325-2327.

5. Kulpreecha, S., Boonruangthavorn, A., Meksiriporn, B. and Thongchul, N. 2009. Inexpensivefed-batch cultivation for high poly(3-hydroxybutyrate) production by a new isolate of Bacillusmegaterium. Journal of Bioscience and Bioengineering.107: 240-245.

6. Nath, A., Dixit, M., Bandiya, A., Chavda, S. and Desai, A.J. 2008. Enhanced PHB production and scaleup studies using cheese whey in fed batch culture of Methylobacterium sp. ZP24. BioresourceTechnology. 99: 5749-5755.

7. Sun, Z., Ramsay, J.A., Guay, M. and Ramsay, B.A. 2007. Carbon-limited fed-batch production ofmedium-chain-length polyhydroxyalkanoates from nonanoic acid by Pseudomonas putida KT2440.Applied Microbiology and Biotechnology. 74: 69-77.

8. Yamane, T. and Shimizu, S. 1984. Fed-batch techniques in microbial processes. Advances in BiochemicalEngineering/Biotechnology. 30: 147-194.


A-5

Bioproduction of Short-Chain-Length-co-Medium-Chain-Length-Polyhydroxyalkanoate from Crude Glycerol

by Engineered Escherichia coli.

Chitwadee Phithakrotchanakoon1, Verawat Champreda2, Sei-ichi Aiba3, Kusol Pootanakit1

and Sutipa Tanapongpipat2

1 Institute of Molecular Bioscience, Mahidol University, Nakhon Pathom Thailand.2 Technology Unit, National Center for Genetic Engineering and Biotechnology Pathumthani Thailand3 Biological Substance Engineering Research Group, Bioproduction Research Institute,

National Institute of Advanced Industrial Science and Technology, Tsukuba Japan

Polyhydroxyalkanoates (PHAs) are potential alternative bio-plastics for conventionalpetrochemical plastics. However, the usage of PHAs in the commodity market is limited due tohigh production cost. Crude glycerol, a by-product from biodiesel production, presents as aninexpensive carbon substrate.

Thus, the aim of this study is to establish the biosynthesis pathway of Short-Chain-Length-co-Medium-Chain-Length-PHAs0(SCL-co-MCL-PHAs)0in recombinant E.coli andto investigate the production of SCL-co-MCL-PHAs by using crude glycerol as substrate.First, the polyhydroxybutyrate (PHB) synthesis pathway was established0by introduction ofrecombinant plasmid pET-phaABCs into E.coli. β-ketothiolase (phaA) and acetoacetyl-CoAreductase (phaB) were cloned from Ralstonia eutropha while PHA synthases (phaCs) werefrom three bacterial strains: Ralstonia eutropha, Aeromonas hydrophila, or Pseudomonasputida. The ability for PHB synthesis was investigated by using 2% glycerol as carbon source.HPLC analysis revealed that the recombinant E. coli harboring PhaAB from R.eutropha andPhaC from R. eutropha or A. hydrophila or P. putida accumulated PHB at the content of24%, 36% and 0%, respectively. Next, the pathway for MCL-monomers generation wasconstructed by introducing enoyl-CoA hydratase (phaJ) into E.coli. phaJ genes wereselected from P.putida and A. hydrophila. They were cloned into pCDFDuet plasmid(pCDF-phaJs) and co-transformed with pET-phaABCs. Protein expression profiles andwestern blot analysis showed that PhaJ of P.putida (PhaJ

p) can be co-expressed with PhaABCs.

Then the ability for SCL-co-MCL-PHAs biosynthesis in recombinants will be explored byusing glycerol and sodium laurate as substrates.

Reference:1. Mothes G, Schnorpfeil C, Ackermann JU. Eng in Life Sci 2007, 7: 475–479


A-6

1,3-propanediol (PDO) Production via Raw GlycerolFermentation for Bioplastic Sheet

Anchana Pattanasupong1*, Sirorat Tungsatitporn1, Sutthirak Meeploy1 andRommanee Wangdeetham2

1 Bioscience Department, Thailand Institute of Scientific and Technological Research, TISTR2 Energy Department, TISTR.* Corresponding author: [email protected]

1,3-Propanediol (PDO) was produced by Enterobacter radicincitans TISTR 1805using crude glycerol; by product from bio-diesel production process. PDO production wasscaled up to 150 L basal medium containing 5% crude glycerol in 300 L fermentor for 3 days.The PDO yield was about 340 mmol mol-1 pure glycerol. After that, the culture product waspassed through purification process by diatomite filtration and fractional distillation at the rangeof 150-300oC, using the pressure of 10 mmHg. The PDO purity was 98%. Preparationof polypropylene succinate (PPSu) using PDO was carried out by esterification andpolycondensation processes. Then, the PPSu was blended with cellulose acetate and castedfor bioplastic film. The preliminary result of biodegradation test in compost revealed that thisfilm could be degraded 69-85% within 3 months at 58±2oC incubation and non toxicity ofresidues after degradation on animal testing by Daphnia magna

Keywords: 1,3 – Propanediol, Crude glycerol, Enterobacter radicincitans, Biodegradation


A-7

Production of Biopolymer Pullulan from a High-YieldingTropical Strain of Aureobasidium pullulans

Sehanat Prasongsuk, Prissana Mangsa, Pongtharin Lotrakul and Hunsa PunnapayakPlant Biomass Utilization Research Unit, Department of Botany, Faculty of Science,Chulalongkorn University, Bangkok 10330, Thailand

Pullulan is a biopolymer produced from the black yeast Aureobasidium pullulans.This biopolymer can be exploited in food and cosmetic industries. In Thailand, several strainsof A. pullulans were successfully isolated from various habitats. Therefore, in this research,five strains of tropical A. pullulans, CU17, CU20, CU24, CU44 and CU45, were evaluatedfor their pullulan productivity. They were cultured in the production medium using sucrose andpeptone as carbon and nitrogen sources, respectively. A. pullulans CU44 was the bestproducer yielding 34 g/l of pullulan. This strain was subjected to optimization experiment byvarying carbon and nitrogen sources in the production medium, pH and temperature forcultivation. Moreover, the effect of nutrient supplements including olive oil, coconut oil andcoconut milk on pullulan production was also investigated. It was found that A. pullulansCU44 gave the highest pullulan at 42 g/l in the medium containing sucrose and peptonesupplemented with olive oil (5% v/v) with initial pH at 6.5 and cultivation at room temperature.


A-8

Double Induced Mutation of Aureobasidium pullulansUsing Gamma Irradiation and EMS

Jirayu Jarassiriprapa, Tuenchai Kosakul, Sehanat Prasongsuk and Hunsa PunnapayakPlant Biomass Utilization Research Unit, Department of Botany,Chulalongkorn University, Bangkok, Thailand 10330.

Induced mutation of Aureobasidium pullulans NRM2 isolated from Thailand, usingirradiation of 2.5 , 3.0 and 3.5 kGy showed the percentage of death to be more than 99% forall radiation levels. Twelve isolates from survived colonies were selected. Comparison of growthbetween different type of variant G12 (3.5 kGy irritated) and control (NRM2) showed radiusof growth colony on Agar plate within 3 day were 1.90 ± 0.03 centimeters and 1.20 ± 0.02centimeters, and the pullulan production were 20.24 ± 2.07 grams per liter and 16.03 ± 0.88grams per liter. respectively. Morever, the next inducced mutation of isolate G12 usingEthylmethane Sulfonate concentration of 3% volume by volume found that the survival rate of20% which. Additional comparisons to G12 and NRM2, that result showed G12E14 = 19.95± 0.58 grams per liter, G12E22 = 20.44 ± 1.16 grams per liter, G12E24 = 19.47 ± 0.84grams per liter and G12E30 = 19.62 ± 0.97 grams per liter for pullulan production showedthat isolate GE12E22 from gamma and EMS induced mutation was the most produces pullulaneffective. G12E14, G12E22, G12E24 and G12E30 when compared to NRM2, the resultsshowed statistically significant for pullulan production, but no significance of G12 (singlemutation using only irradiation). The Mutants colonies from double mutation of G12E14,G12E22, G12E24 and G12E30 (induced mutation using irradiation and chemical mutagen:EMS) were strongly stability production of pullulan, in the opposite way , the result from singlemutation by irradiation of G12 is not stable of pullulan production.

Keywords: induced mutation, irradiation, chemical mutagen EMS, Aureobasidium pullulans,


A-9

Purification of Succinic acid from Synthetic SolutionsUsing Esterification Coupled with Reactive Distillation

Technique

Sebastien Molina1, Apichat Boontawan1,*

1 School of Biotechnology, Institute of Agricultural Technology Suranaree University of Technology,Nakhon Ratchasima, Thailand 30000

* corresponding author. Tel: +(66) 44-224234; Fax: +(66) 44-224154 E-mail: [email protected]

Until recently, most of the plastics have been manufactured from petrochemicals, andare not biologically degradable. The potential of biodegradable polymers and moreparticularly of polymers obtained from agro-resources have long been recognized. Succinicacid is used as a monomer to produce biobased polybutylene succinate (PBS), which later hasdeveloped application as degradable bioplastic. In this work, an aqueous solution containingsuccinic acid, formic acid, acetic acid, and lactic acid with the concentrations of 420, 50, 40,and 10 g/L was employed as the model solution. The solution (4 L) was acidified with sulfuricacid, and was pumped into a 15 L reactor followed by an addition of the equal volume ofanhydrous ethanol. The solution was heated and the esterification reaction was commencedby an introduction of 2% sulfuric acid (w/v). A highly efficient fractionating column designed inour laboratory was employed to shift the conversion beyond the thermodynamic equilibriumconversion by continuous removal of water from the reactor as distillate. In addition, a vaporpermeation technique using a commercial NaA zeolite tubular membrane was successfullyemployed to dehydrate the distillate before returning the dehydrated ethanol into the reactor.This integrated esterification-distillation process allowed a complete conversion of organicacids to the corresponding esters. Due to their much different boiling points, diethyl succinatewas completely separated from the other esters by using a vacuum fractionation technique.Finally, a high purity of succinic acid can be produced simply by hydrolysis using deionizedwater with Amberlyst-15 as the catalyst.

Keywords: Succinic acid, Esterification, Reactive distillation, Hydrolysis.


A-10

Study of the Thermal Properties of Rectangular Barsof Poly (lactic acid) Stereocomplexes

Suppamart Ngenruangroj and Amornrat LertworasirikulDepartment of Materials Engineering, Faculty of Engineering, Kasetsart University, Bangkok, Thailand, 10900Tel : +662-942-8555 ext 2128, Fax : +662-955-1811, [email protected]

Our research aims to investigate the thermal properties of poly (lactic acid)stereocomplex products. In this study, poly (lactic acid) stereocomplex compounds wereprepared in an internal mixer. Formation of poly (lactic acid) stereocomplex (PLASc) wasconfirmed by X-ray diffraction (XRD) and differential scanning calorimetry (DSC) techniques.The stereocomplexes showed glass transition temperatures ranging from 50-56oC, andmelting temperatures ranging from 200-215oC. The addition of ester plasticizer (5-50%)lowered the glass transition temperatures, and melting temperatures of the stereocomplexesabout 6oC, and 10oC, respectively. The compounds were shaped into rectangular bars througha compression molding process. Thermal stability of the rectangular bars was determined byuse of the vicat softening test. The obtained products showed vicat softening temperatures(Tvicat) around 130-140oC, which are 90oC higher than Tvicat of typical poly (lactic acid). Thebars maintained their original shape after being subjected to microwave radiation for 5 minutes.

References:1. F. Carrasco, P. Pagesb, J. Gamez-Perez, O.O. Santana and M.L. Maspoch, Polym. Degrad. Stab. 95

(2010) 116-125.2. L. V. Labrecque, R.A. Kumar, V. Dave, R. A. Gross, J. Appl. Polym. Sci. 66 (1997) 1507–1513.3. N. Rahman, T. Kawai, G. Matsuba, K. Nishida, T. Kanaya, H. Watanaba, H. Okamoto, A. Usuki, M.

Matsuda, K. Nakajima, N. Honma, Macromol. 42 (2009) 4739-4745.4. S. Ferguson, D. Wahl, S. Gogolewski, J. Biomed. Mater. Res. 30 (1996) 543-551.

Acknowledgement:This study was supported by a grant from the National Innovation Agency (NIA).


A-11

Linear/star-shaped Poly(L-lactide) Blends SynthesizedThrough Single-Step ring-Opening Polymerization

Yodthong Baimark*, Yaowalak SrisuwanDepartment of Chemistry, Faculty of Science, Mahasarakham University, Mahasarakham 44150, Thailand*Corresponding author. E-mail : [email protected]

In recent year, there has been an increasing interest in star-shaped poly(L-lactide)s(PLLs), which are branched polymers distinguished by a structure containing three or morelinear arms radiating from a center. The star-shaped PLLs are expected to display peculiarviscosity, thermal and mechanical properties, and degradation profiles compared with linearPLL. Polymer blending is an effective method that has been widely used to adjust theproperties of polymers. Thus, unique properties of polymer blends quite different from theirorigin polymers were obtained. However, melt blending of linear and star-shaped PLLsinduced their thermal degradation. The purpose of this work is to prepare the linear/star-shaped PLL blends via the single-step ring-opening polymerization. The linear/star-shapedPLL blends were synthesized using stannous octoate and 1-dodecanol/pentaerythritol mixtureas the initiating system. Usually, the 1-dodecanol and pentaerythritol contained one and fourhydroxyl end groups were used for polymerizing the linear and star-shaped PLLs,respectively. The linear/star-shaped PLL blends with linear PLL/star-shaped PLL blend ratiosof 4/1, 2/1, 1/1 and 1/2 (w/w) were prepared by varying the 1-dodecanol/pentaerythritol moleratio. Intrinsic viscosity of PLL blends increased significantly as the pentaerythritol mole ratio(or the star-shaped PLL blend ratio) increased. Crystallinity and thermal stability of PLL blendsdecreased but glass transition and melting temperatures did not change as the star-shaped PLLblend ratio increased. Mechanical test and in vitro biodegradation of these linear/star-shapedPLL blend films are under investigation.

Keywords: Linear PLL; star-shaped PLL; polymer blends; viscosity; thermal properties


A-12

Synthesis of PolylactideUsing Bis(amidinate)tin(II) Complexes.

Parichat Piromjitpong, Khamphee Phomphrai*Center for Catalysis, Department of Chemistry and Center for Innovation in Chemistry,Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400 Thailand.*Corresponding author. Tel.:0-2201-5146; Fax: 0-2354-7151 E-mail: [email protected]

Biodegradable polymers derived from inexpensive renewable resources have receivedtremendous attentions during the past decade. Examples of biodegradable polymers includepolylactide, polyglycolide, and poly(ε-caprolactone). Such polymers have been synthesizedmostly using ligated metal complexes. Thus, great efforts have been made to understand thepolymerization process and how catalysts interact with the monomers. Our research groupfocuses on the development of new catalysts for the polymerization of several cyclic esterssuch as lactide and ε-caprolactone leading to biodegradable polymers. The catalysts aredesigned having Tin(II) as an active metal ligated by amidine ligands. We have modified theligands systematically by changing the electronic and steric influences to tailor the catalyticperformance. The application in the polymerization of lactide will be discussed.


A-13

Effect of Talc Particle Size on CrystallizationBehavior of Polylactic Acid

Paveena Prachayawasin* Nukul Euaphantasate Suvit Uasopon and Wisaroot PayubnopNational Metal and Materials Technology Center *Corresponding author: [email protected]

This research was to study the effect of talc particle sizes on crystallization behavior ofpolylactic acid (PLA). The poly(lactic acid)/talc composite (PLA/talc) with 10% weight oftalc was successfully prepared with a twin screw extruder. Three particle sizes of talc, i.e., 0.8,1.1 and 2.3 micron were used. The non-isotharmal crystallization behavior of PLA/talccomposites was determined by differential scanning calorimetry (DSC). The DSC results showedthat degree of crystallinity (x

c) at 90oC of PLA/talc composites with different talc particle sizes,

i.e., 0.8, 1.1 and 2.3 micron was 15.8, 13.0 and 15.6% respectively. There were no significantdifferences, in terms of x

c, among the particle sizes of talc. In addition, the crystallization half

time at 90oC of PLA/talc composites with different particle sizes, i.e., 0.8, 1.1 and 2.3 micronwas 5.5, 7.9 and 8.5 minutes, respectively. It was concluded that the smaller particle sizes oftalc were employed, the higher the rate of the composites crystallization were resulted. This isbecause the higher of amount of talc particles and surface areas resulted in the higher rate ofcrystallization.

Keyword: Polylactic acid (PLA), talc, particle size, crystallization half time

Figure 1 Relationship between relative crystallinity


A-14

Multi-Branched Poly (Lactic Acid): A NovelApproach for Enhancing PLLA Crystallization

from Biobased Compounds

Yupin Phuphuak1, Piyawanee Jariyasakoolroj1, Yong Miao3,4, Philippe Zinck3,4,*

and Suwabun Chirachanchai1, 2,*

1 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, Thailand2 Center for Petroleum, Petrochemical, and Advanced Materials, Chulalongkorn University, Bangkok, Thailand3 Universit� Lille Nord de France, F-59000 Lille, France4 ENSCL, UCCS, CCM, F-59652 Villeneuve d’Ascq, France*Corresponding authors E-mail: [email protected] and [email protected]

Poly(lactic acid)(PLA) is one of the most commercially important biodegradable andbiocompatible polymers, exhibiting a wide array of applications in packaging and biomedicalfields. However, PLA exhibits low crystallization rate in comparison with conventional plastics,and the limitations related to the brittleness obstruct the practical uses. Some advancedapproaches such as introducing branched structure into PLA or blending it with dendritichyperbranched polymers have been reported for enhancing the crystallization of PLA [1].Another advanced approach is the use of an enantiomeric mixture of PLLA and PDLA to forma stereo-complex which accelerates the PLA crystallization [2]. However, the low cost and thesimplicity of preparation are still the points to be considered. In the present work, we introducethe use of multi-branched PLLA based on various core molecules (succinic acid, malic acidand citric acid as di-, tri, and tetra-functional core molecules) to accelerate the crystallization ofPLLA. We found that they act as excellent nucleating agents of PLLA as they induce very smallspherulites and increase the crystallization rate of PLLA effectively. The crystallinity of PLLA isalso found to be enhanced with increasing the numbers of branches. Furthermore, the use ofcarbohydrates derivatives seems relevant to this case, as carbohydrates are renewable resources,biocompatible and biodegradable compounds [3]. The use of carbohydrates is thus consideredas initiators for the synthesis of star-functionalized polymers. Herein, we present further thesynthesis of multi-branches of PLLA by using carbohydrate derivatives as a core molecule forthe functionalization of polylactides via organocatalyzed ring-opening polymerization.

References:1. J.F. Zhang; X. Sun, Polym Int 2004, 53, 716.2. T. Ouchi; T.Kontani; Y. Ohya, Polymer 2003, 44, 3927.3. Y. Miao; C. Rousseau; A.Mortreux; P. Martin; P. Zinck, Polymer 2011, 52, 5018.

Acknowledgments:One of the authors (Y.P.) wishes to thank the Strategic Scholarship Fellows Frontier

Research Networks for the Ph.D. scholarship.


A-15

Synthesis of Poly(D-lactic acid)Using Direct Polycondensation Process

Weraporn Pivsa-Art, Somridee Laksanajun, Rutchaneekorn Wongpajan and Sommai Pivsa-ArtDepartment of Chemical and Materials Engineering, Faculty of Engineering, Rajamangala University ofTechnology Thanyaburi, Pathumthani, 12110 Thailand

This research aimed to study the synthesis of biodegradable poly (lactic acid) usingdirect-condensation polymerization method. The processes comprised of 3 steps: dehydration,melt polymerization and solid-state polymerization. D-Lactic acid was used as startingmaterial. The first step is dehydration at 180oC with pressure 30 torr for 2 h. The first stepproduct produced was viscous pre-polymer. The pre-polymer was then subjected toMelt-polymerization using 0.5 wt% SnCl

2.2H

2O) and p-Toluenesulfonic acid, p-TSA at 180oC,

10 torr for 5 h. The white solid, oligomer of D-lactic acid, was further subjected to increase itsmolecular weight using solid state polymerization process at 165oC, pressure 10 torr for 30 h.The synthesized poly(D-lactic acid) was subjected to analyzed the thermal property andmolecular weight.

Poly(D-lactic acid) was synthesized from D-lactic acid using a two steps directpolycondensation. The first step comprised of dehydration from esterification reaction andtrans-esterification. p-Toluenesulfonic acid was used as a catalyst. The products from the firststep called pre-polymers were subsequently subjected to solid-state polymerization (SSP)under high temperature and reduced pressure. Prior to the SSP process, the pre-polymerswere characterized their thermal property to detect their crystallization temperature (Tc). Thepre-polymers were annealed at temperature Tc for 2 h until the crystallization peakdisappeared. The SSP of pre-polymers was carried out for 30 h to produce the satisfiedthermal property and high molecular weight. The synthesized poly(D-lactic acid) showedmelting temperature of 177oC, weight average molecular weight of 33,300 Da, anddecomposition temperature of 255oC. The synthesized PDLA can be applied to prepare thestereocomplex with poly(L-lactic acid) for high temperature utilization polymers.

Keywords: Direct polycondensation, Biodegradable polymers, Poly(D-lactic acid)

References:1. Zhang, L., S. H. Goh and S. Y. Lee, “Miscibility and crystallization behavior of poly(L-lactide)/

poly(p-vinylphenol) blends” Polymer, 39, 4841-4847 (1998).2. Lunt, J., “Large-scale production, properties and commercial applications of Polylactic acid polymers”

Polym. Degrad. Stab. 59, 145-152 (1998).


A-16

Synthesis of D-Lactide and Poly(D-Lactide)Using Novel Catalyst / Initiator System

Winita Punyodom1, Puttinan Meepowpan1, Kanarat Nalampang1 and Robert Molloy1,2

1 Polymer Research Group, Department of Chemistry, Faculty of Science, Chiang Mai University,Chiang Mai, Thailand 50200

2 Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai, Thailand 50200E-mail: [email protected]

The synthesis of D-lactide and poly(D-lactide) from D-lactic acid in terms of both% yield and purity has been developed using novel catalyst / initiator system. The preparationof D-lactide comprises a two-step reaction: (1) polycondensation of D-lactic acid (74 %w/w)using conventional catalyst (tin(II) octoate, Sn(Oct)

2) or novel catalyst A to obtain low

molecular weight poly(D-lactic acid), PDLA, followed by (2) thermal decomposition of thelow molecular weight PDLA under vacuum to yield crude D-lactide. The temperature,pressure and type and amount of catalyst had significant effect on the % yield of D-lactide.From the results obtained, the novel catalyst A was found to be the more efficient overall,giving a very high % yield of D-lactide (99% crude, 75% purified) in high optical purity(GC-MS; 95.54% crude and 100% purified, Optical Purity (% R) = 92.82) over a shortreaction time (11 hours) when using the suitable condition. The composition of crude D-lactideproduced from D-lactic acid using novel catalyst A is D-lactide (95.54%) and D-lactic acidmonomer (4.46%). The results show that a one-pot novel catalyst can effectively promoteboth the polycondensation and the thermal decomposition steps. The crude D-lactide wasthen purified by repeated recrystallization from ethyl acetate and then was subsequently usedas monomer for the production of controlled molecular weight poly(D-lactide), PDL via thering-opening polymerization (ROP) in bulk using Sn(Oct)

2 or catalyst A as the initiator using

various conditions. Both high yields (> 95%) and controlled molecular weights (Mv = 1.0x104

- 1.5x105 and [η] = 1.0-3.0 dl/g in chloroform at 25�C) were obtained depending on thereaction temperature and time, type and amount of initiator used. The structure and propertiesof PDL were confirmed by FTIR, 1H-NMR and DSC. These results clearly demonstrate thatnovel Catalyst A has the dual advantage of being both an effective one-pot catalyst forD-lactide synthesis and an effective initiator for D-lactide polymerization.

References:1. M. Dumklang, N. Pattawong, W. Punyodom, P. Meepowpan, R. Molloy, M. Hoffman, Chiang Mai

Journal of Science, 36(2), 136-148 (2009).2. M. Jalabert, C. Fraschini and R.E. Prud’Homme, Journal of Polymer Science Part A: Polymer Chemistry,

45, 1944-1955 (2007).3. L. Feng, X. Bian, Z. Chen, X. Chen, G. Li, Polymer Testing, 30(8), 876-880 (in press).


A-17

A Pilot Scale Synthesis of Poly(L-lactic acid)Using a Direct Polycondensation Method

Sommai Pivsa-Art1, Sorapong Pavasupree1, Weraporn Pivsa-Art1, Sumonman Niamlang1,Kiyoaki Ishimoto2 and Hitomi Ohara2

1 Department of Chemical and Materials Engineering, Faculty of Engineering, Rajamangala Universityof Technology Thanyaburi, Klong 6, Thanyaburi, Pathumthani, Thailand

2 Department of Biobased Materials Science, Kyoto Institute of Technology, Kyoto, Japan

Poly(L-lactic acid) was synthesized using direct polycondensation process of L-lacticacid. The process was developed from conventional 3 steps using SnCl

2×2H

2O) 0.5% and

p-Toluenesulfonic acid as co-catalysts into 2 steps synthesis. The first step involved meltpolycondensation using p-Toluenesulfonic acid as a single catalyst. The pre-polymer productfrom the first step was subjected to annealing at the crystallization temperature (Tc) for 2-3 h.The annealed pre-polymers were subjected to solid-state polymerization. The poly(L-lacticacid) synthesized showed Tm at 172oC, molecular weight more than 30,000 Da anddecomposed at 312oC. The data of laboratory scale synthesis was applied to a pilot scale testrun at Hitachi Plant Technologies, Ltd. and Hosokawa Micron Corporation. The PLLAproducts after SSP at 135oC, 3h, showed Tm of 161oC. The data of PLLA synthesis was usedto design the pilot plant for construction of the pilot plant. The test run for pilot scale is plannedto operate with the pilot plant.

Keywords: Poly(L-lactic acid), biodegrdadable polymers, pilot plant, melt polycondensation,solid state polymerization

References:1. K. M. Nampoothiri, N. R. Nair, R. P. John, “An overview of the recent developments in polylactide

(PLA) research”, Bioresource Technology 101, 8493–8501 (2010).2. T. Maharanaa, B. Mohantyb, Y.S. Negi, “Melt–solid polycondensation of lactic acid and its

biodegradability”, Progress in Polymer Science, 34, 99–124 (2009).3. S. Yodaa, D. Brattonb, S. M. Howdleb, “Direct synthesis of poly(L-lactic acid) in supercritical carbon

dioxide with dicyclohexyldimethylcarbodiimide and 4-dimethylaminopyridine”, Polymer 45 7839–7843(2004).


A-18

Synthesis of TiO2 Impregnated Bacterial Cellulose forPhotocatalytic Decomposition and Antibacterial Applications

Nattakammala Janpetch1, Seiichi Tokura3, Ratana Rujiravanit1, 2

1 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, THAILAND2 Center for Petroleum, Petrochemicals, and Advanced Materials, Chulalongkorn University,

Bangkok 10330, THAILAND3 Faculty of Chemistry, Materials, and Bioengineering, Kansai University, Osaka, JAPANE-mail: [email protected]

Nowadays, toxic, dye and germ contamination in water generated from industries hasbecome a serious pollution problem. Several treatments have been proposed to solve theproblem including the use of photocatalyst via photocatalytic reaction. Photocatalytic reactionhas been reported to be an efficient method to treat various toxic substances as well aspathogenic microorganisms. Among the inorganic photocatalysts, TiO

2 has proven as the most

promising photocatalyst capable of utilizing for widespread environmental applications. In thisstudy, TiO

2 were impregnated into bacterial cellulose (BC) pellicle. Due to its nanoscale size of

fibers, porous structure and high surface area, BC has been expected to be a good support forphotocatalytic reaction of the TiO

2. Methylene blue, a basic dye, was used as a model to

determine photocatalytic efficiency of the TiO2 impregnated bacterial cellulose on the

methylene blue removal. In addition, antibacterial activity against S. aureus, a gram positivebacterium, and E. coli, a gram negative bacterium, of the TiO

2 impregnated bacterial cellulose

was also investigated.

References:1. Yamanaka, S., Watanabe, K., Kitamura, N., Iguchi, M., Mitsuhashi, S., Nishi Y. and Uryu, M. (1989), The

structure and mechanical properties of sheets prepared from bacterial cellulose, Journal ofMaterials Science, 24, 1573-4803.

2. Herrmann, J.M. (1999), Heterogeneous photocatalysis: fundamentals and applications to theremoval of various types of aqueous pollutants, Catalysis Today, 53(1), 115-129.

3. Fujishima, A., Rao, T.N. and Tryk, D.A. (2000), Titanium dioxide photocatalysis, Journal ofPhotochemistry and Photobiology C: Photochemistry Reviews, 1(1), 1-21.


A-19

Effect of Heat Pretreatment and Acremonium cellulolyticusEnzymes on Saccharification of Cassva Pulp

Sirapan Sukontasing1* and Hiroyuki Inoue2

1 Faculty of Veterinary Technology, Kasetsart University 50 Ngam Wong Wan, Ladyao, Chatuchak,Bangkok 10900 Thailand Tel:+66-2579-8574 Fax +66-25798571 E-mail: [email protected]

2 Biomass Technology Research Center (BTRC) National Institute of Advanced Industrial Science andTechnology (AIST) 3-11-32, Kagami-yama, Higashi-hiroshima, Hiroshima 739-0046, Japan

The aim of this study was to examine the effectiveness of heat pretreatment andenzymatic saccharification of cassava pulp (CP). Solka Floc (SF) and CP were used as solecarbon sources for cellulase production by mutant strains of Acremonium cellulolyticus,CF-2612 and TN. Four types of crude enzyme supernatants derived from different strains andcarbon sources named CF-CP, CF-SF, TN-CP and TN-SF were collected. Filter-paper(FPase), Carboxymethylcellulase (CMCase), Amylase, alpha- and beta- glucosidase specificactivities of the crude enzymes were analyzed. SF cultures exhibited higher cellulase activitiesthan CP cultures while amylase activities were low both in CF-SF and TN-SF. Saccharificationabilities of CP and autoclaving heat pretreatment CP by the four crude enzymes andcommercial enzyme Acremonium cellulase (CA) were comparatively analyzed. CF-CPenzymes derived from A. cellulolyticus strain CF-2612 cultured in CP containing media gavehigh sugars conversion rate of 37.36% glucose, 51.65% galactose and 49.68% arabinosefrom 1 mg enzyme culture per g CP. Saccharification of heat pretreatment of CP by the CF-CPenzyme exhibited a 2-fold higher glucose conversion rate than that of non-treatment CP.CF-CP enzyme was more efficiently than TN and the CA on hydrolysis of CP, even though itshown low activities of cellulases. Combination of CP and SF enzymes had no effect onimprovement of saccharification of CP.

Keywords: Pretreatment, Saccharification, Cellulase, Cassava pulp


A-20

Sugar Production from Rice Straw Using CombinedChemical and Biological Treatment

Metinee Wasoontharawat and Sunthorn Kanchanatawee*School of Biotechnology, Institute of Agricultural Technology, Suranaree University of Technology,Muang District, Nakhon Ratchasima 30000 *Corresponding author: [email protected]

Rice straw is one of the lignocellulosic materials in which it is readily available inSouth-East Asia countries. It would exhibit a great potential as a fermentative substrate forfuels and chemicals because of its high carbohydrate content (66%) containing 39% cellulose,27% hemicellulose, and 12% lignin. In this study, the production of sugars from chopped ricestraw (~1 cm) via combined treatments of chemicals and fermentation by Clostridiumcellulolyticum DSM 5812 was investigated. Differences in chemical pretreatment of the ricestraw sample were carried out by adding the sample in each of these chemical solutions: 0.5%H

2SO

4, 2% NaOH, or water, and the solutions were heated at 121�C for 60 minutes. These

pretreated rice straws were further used as cellulosic substrates for a biological hydrolysis byCl. cellulolyticum . The results showed that Cl. cellulolyticum DSM 5812 were able todegrade all pre-treated rice straw samples at 35oC under anaerobic conditions. The strain wasable to utilize and release sugars from all of the pretreated rice straws in which the hydrolysatecontained a mixture of sugars such as cellobiose, glucose, xylose and arabinose. The highestsugar concentration of 12.44 g/L was achieved from the alkaline pretreated rice strawhydrolyzed by Cl. cellulolyticum DSM 5812 after 16 days at 35oC under anaerobicconditions. Whilst the sugar productions from untreated, water pre-treated, and acidpre-treated rice straws were 1.99, 1.68, and 1.44 g/L, respectively. Therefore, the alkalinepre-treatment of the chopped rice straw followed with fermentation by Cl. cellulolyticumDSM 5812 was an efficient method for sugar production from a rice straw.

Keyword: Sugar production, Rice straw, Cellulose fermentation, Clostridium cellulolyticum


A-21

Application of Thermophilic Enzymes andWater Jet System to Cassava Pulp

Siriporn Chaikaew1, Kota Ogura2, Gaku Sugino2, Yuka Maeno3, Seung-Hwan Lee3 andKazuhiko Ishikawa3

1 Department of Food Technology, Faculty of Agro-Industry, Prince of Songkla University, Had Yai,Songkla 90112, Thailand

2 Sugino Machine Limited, 2410, Hongo, Uozu, Toyama 937-8511, Japan3 National Institute of Advanced Indrustrial Science and Technology (AIST), Biomass Technology

Research Center, 3-11-32, Kagamiyama, Higashi-hiroshima, Hiroshima 739-0046, Japan

Star Burst System (SBS) made by Sugino Machine Limited is a unique atomizationmachine using water jet that puts low stress on environment. SBS provides a mild treatmentsystem for effectively subsequent saccharification for biomass with the combination of themulti-enzyme activity. In this study, we tried to atomize and saccharify the cassava pulp usingSBS and thermophilic enzymes. A high yield of fermentable sugars was obtained after 24 hrincubation at 85oC and pH 5.5 using SBS and the thermophilic multi-enzyme system.Moreover, fine nanofibrillated cellulose was produced by the presence of the thermophilicenzyme. The combination of SBS and thermophilic enzymes can be applicable for theproduction of fermentable sugars and fine nanofibrillated cellulose from cassava pulp.Furthermore, this process will be applicable for production of various bio-products ofeconomic importance.

Keywords: Water jet, Biomass, Cellulose, Cassava pulp, Nanofiber, Thermophilic enzyme

References:1. Watanabe, Y., Kitamura S., Kawasaki, K., Kato, T., Uegaki, K. Ogura K. and Ishikawa, K. Application of

a water jet system to the pretreatment of cellulose. Biopolymers. 1-7 (2011 in press).2. Lee, S.H., Chang F., Inoue S., Endo, T. Enzymatic saccharification of woody biomass micro/nanofibrillated

by continuous extrusion process II: Effect of hot-compressed water treatment. Bioresour. Technol.101, 9645-9649 (2010).

3. Rattanachomsri, U., Tanapongpipat, S., Eurwilaichitr, L. and Champreda, V. Simultaneous non-thermalsaccharification of cassava pulp by multi-enzyme activity and ethanol fermentation by Candidatropicalis. J. Biosci. Bioeng. 107, 488-493 (2009).


A-22

Development of Biomass Conversion ProcessUsing Water Jet and Hyperthermophilic Cellulase

Yuka Maeno & Kazuhiko IshikawaNational Institute of Advanced Industrial Science and Technology (AIST) Biomass Technology ResearchCenter (BTRC) 3-11-32, Kagamiyama, Higashi-hiroshima, Hiroshima 739-0046, Japan

Cellulose related biomass produced from plants is the most abundant organiccompound on earth. The technology for the biomass to produce cellulose fiber or fermentablesugars holds the key to the application of biomass. Cellulase is an enzyme involved in thedegradation of beta-glucan cellulose biomass. Hyperthermophilic cellulase would beparticularly useful in the industrial applications of biomass. We recently isolated hyperthermophiliccellulases from hyperthermophilic archaea and characterized them [1-3]. These enzymes havethe potential for the biomass saccharification at high temperature. On the other hand, we arealso awaiting the mild atomizing procedure (pretreatment) of biomass. A number ofpretreatment procedures have been developed. Out of these methods, sulfuric acid treatment,steam explosion, hot-compressed water treatment, lime pretreatment and ammoniapretreatment are known to be the effective methods. However, most of them have theindividual disadvantages for their applications. Water jet is a well known mild machine appliedfor washing machine, cutter and mill using the high pressure of water. We first tried to use thewater jet system to the atomization and pretreatment of biomass [4]. Using the water jetsystem and hyperthermophilic cellulases, we developed a new system of biomass applicationfor saccharification and production of cellulose nanofiber.

References:1. S. Ando et al., Applied and Environmental Microbiology, vol.68 pp430-433, (2002)2. H. Kim and K. Ishikawa, Proteins, vol.78, pp496-500 (2010)3. H. Kim and K. Ishikawa, Biochemical Journal (2011) in press4. Y. Watanabe et al., Biopolymers (2011) in press


A-23

Chitosan Nanoscaffold Gel via Water-basedHeterogeneous System

Noppadol Trirong 1, Suwabun Chirachanchai*,1,2

1 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, Thailand2 Center for Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn University, Bangkok 103303 Center of Innovative Nanotechnology, Chulalongkorn University, Bangkok 10330*Corresponding author E-mail: [email protected]

It is well-known that chitosan is one of the most potential biomaterials with not only thebiodegradability, biocompatibility, and non-toxicity, but also other various unique propertiessuch as complexation with metal ions for environmental purposes, antimicrobial activities forhealth care related products, tissue and cell compatibilities for biomedical uses, etc.1-3

Currently, our group succeeded in developing a novel material, so-called chitosan nanoscaffoldwith nanopores structure. As the scaffold network is an important structure for artiucial organs,extracellular matrices, implantations, etc4, the gel scaffold might be a material to be satisfiedwith all requirements. However, the fact that chitosan dissolves only in acid, the toxicity isalways the problem. Thus, the present work proposes a novel approach to prepare chitosannanoscaffold gel by using water-based heterogeneous reaction between chitosan nanoscaffoldand epichlorohydrin. From this system, neither acid nor organic solvent are necessary, whereasnanofibers of chitosan nanoscaffold maintain their networks in hydrogel (Scheme 1). Thepresentation covers the reaction details and characterization results including the discussion onthe factors related to gelation time, and thermal stability of the materials.

Scheme 1

Acknowledgments:Research, Development and Engineering (RD&E) fund through The National

Nanotechnology Center (NANOTEC), The National Science and Technology DevelopmentAgency (NSTDA), Thailand (Project No. NN-B-22-FN1-10-52-14) to the Petroleum andPetrochemical College.

References:1. Richardson, S.C., Kolbe, H.V., and Ducan, R. Int. J. Pharm. 1999, 178, 231-243.2. Rinaudo, M. Prog. Polym. Sci. 2006, 31, 603-632.3. Mirko, X.W., Janelle, C.M., and Jorg, T. Carbohydr. Polym. 2009, 78, 678-684.4. Phongying, S., Aiba, S., and Chirachanchai, S. Polym. J. 2007, 48, 393–400.

<


A-24

Structural Studies on Enzymatic Reaction ofBacterial Copper Amine Oxidase

Misumi Kataoka1, Toshihide Okajima2, Katsuyuki Tanizawa2 and Hiroshi Yamaguchi3

1 National Institute of Advanced Industrial Science and Technology (AIST)2 Institute of Scientific and Industrial Research, Osaka University3 School of Science and Technology, Kwansei Gakuin University

Functions of protein correspond to their structures. X-ray crystallography is a powerfultool for determination almost three-dimensional positions of atoms in enzyme molecules.Observation sequential photographs such as four-dimensional movie, that is, detecting somereaction intermediates at atomic resolution during catalytic reaction and reconstitution thesestructures, give us enough various information to understand reaction mechanism facilely.

Copper amine oxidase contains a covalently quinone cofactor, topaquinone (TPQ),which is generated by post-translational modification of a conserved specific tyrosine residuecontained in the precursor enzyme. The enzyme catalyzes oxidative deamination of variousprimary amines by a Ping-Pong bi-ter mechanism, consisting of reductive and oxidativehalf-reactions. In the former reductive half-reaction, a substrate Schiff-base is formed betweenan amine substrate and the cofactor in the initial oxidized form (TPQ

ox), which is finally

converted to a semiquinone radical form (TPQsq), yielding an aldehyde product. To elucidate

the structure-based reaction mechanism of copper amine oxidase, I have carried outtime-resolved x-ray crystallographic analyses of the reductive half-reaction catalyzed bycopper-containing phenylethylamine oxidase from Arthrobacter globiformis (AGAO). TheAGAO crystals were soaked anaerobically in a solution containing its preferred substrate,phenylethylamine, and frozen in liquid nitrogen at appropriate time intervals to freeze-trap thereaction intermediates transiently formed in the crystals. Before exposure to x-ray, the crystalswere subjected to single-crystal microspectrometry for monitoring the absorption spectrum ofTPQ that reflects its chemical structure. Consequently, crystal structures of four distinctintermediates formed during the reductive half-reaction have been determined. It has beenfound that significant conformational changes of TPQ and several active-site residues locatedin the substrate-binding pocket are associated with the progress of the reductive half-reaction.

Session: B

Downstream (Processing and Application)

Poster Presentation


B-1

Preparation, Characterization and Properties of TernaryBlends with Epoxidized Natural Rubber, Poly (lactic acid)

and Poly (butylene adipate-co-terephthalate)

Tarinee Nampitch1, a and Rathanawan Magaraphan2, b

1 Department of Packaging Technology, Faculty of Agro-Industry, Kasetsart University, Bangkok10900, Thailand.

2 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand.a [email protected], [email protected]

The objective of this work was to study the production of new biodegradable thinfilms. As a result of increasing problems with regard to the disposal of domestic waste,particularly plastics, a new class of polymers especially designed to be biodegradable has beenundergoing development. However these biodegradable plastics still have a limitation, i.e. highcost. This research studied methods of lowering the cost of biodegradable plastic and ofimproving its properties by using epoxidized natural rubber as a another polymer for polymerblends. Thus, ternary blends of epoxidized natural rubber (ENR), poly(lactic acid) (PLA)and poly(butylene adipate-co-terephthalate) (PBAT) were studied and prepared using atwin-screw extruder, followed by use of a chill roll cast film extruder or a blown film extruder,to produce biodegradable film. The concentration of ENR in the ternary blends was fixed at 10wt%, with the remainder being PLA and PBAT. In some proportions of the film blends, Irganoxand Uvinul were introduced to increase the thermal stabilization and UV stabilization,respectively. The mechanical and thermal properties were evaluated, including the thickness,color, and water vapor permeability (WVP) of the biodegradable films.

Keywords: biodegradable plastics, polymer blends, poly(lactic acid), epoxidized naturalrubber, poly(butylene adipate-co-terephthalate)


B-2

The Influence of CaCO3 on Morphology andThermal Stability of PLA Extrusion Sheet

Bawornkit Nekhamanurak1,2, Pajaera Patanathabutr1,2,* and Nattakarn Hongsriphan1,2

1 Department of Materials Science and Engineering, Faculty of Engineering and Industrial Technology,Silpakorn University, Nakhonpathom, Thailand (E-mail: [email protected])

2 Center of Excellence for Petroleum, Petrochemicals, and Advanced Materials, ChulalongkornUniversity, Bangkok, Thailand

In recent years, Poly(lactic acid) (PLA) has become one of most interestingbiopolymers that could offer a potential alternative to petrochemical plastics. Modification ofPLA by additives and fillers has been widely investigated in order to obtain desired propertiesfor various applications. This study aims to investigate effect of particle size (micro- ornano-scale) and particle loading of calcium carbonate (CaCO

3) on morphology and thermal

stability of PLA-CaCO3 extrusion sheet. PLA pellets were melt compounded with micro- and

nano-sized CaCO-3 particles using a twin-screw extruder and PLA-CaCO

3 extrusion sheets

were fabricated. From scanning electron microscopy (SEM) micrographs in figure 1, it isfound that good dispersion of CaCO

3 particles in PLA matrix was achieved for both

micro- and nano-sized CaCO-3-PLA extrusion sheets. X-ray diffraction (XRD) patterns

indicated that micro- and nano-sized CaCO3 coated with fatty acid inhibited the crystallization

of PLA matrix. And, thermo gravimetric analysis (TGA) results reveal that adding CaCO3

particles reduce thermal stability of PLA composites which nano-sized CaCO3 particles

affected thermal stability of PLA composites more than those added micro-sized CaCO3

particles. This is related to the higher amount of coating substance on larger surface area of thenanoparticles.

Figure 1 SEM micrographs of micro- and nano-sized CaCO3-PLA composites

with fillers of 5 wt% loading

References:1. T.D. Lam, T.V. Hoang, D.T. Quang, J.S. Kim, Materials Science and Engineering: A 501 (2009) 87-93.2. L.-T. Lim, R. Auras, M. Rubino, Progress in Polymer Science 33 (2008) 820-852.3. S. Sinha Ray, M. Bousmina, Progress in Materials Science 50 (2005) 962-1079.4. S. Miao, Applied Surface Science 220 (2003) 298-303.5. M. Avella, S. Cosco, M.L.D. Lorenzo, E.D. Pace, M.E. Errico, G. Gentile, European Polymer Journal 42

(2006) 1548-1557.


B-3

Development and Thermal Behavior of Carboxymethyl-cellulose/Polylactic Acid Composite Films

Chamaiporn Yamoum1, Rathanawan Magaraphan*1,2 The National Center of Excellence for Petroleum, Petrochemicals and Advanced Material2 Polymer Processing and Polymer Nanomaterials Research Unit, Petroleum and Petrochemical [email protected]

Carboxymethylcellulase (CMC) was mixed with polylactic acid (PLA) in order toform composite by blown film extrusion. The effects of CMC content and plasticizer onthermal, thermo-mechanical and morphological properties were studied. It exhibited that theamount of crystallization can be enhanced due to the presence of CMC content and the glasstransition temperature was decreased due to the addition of triacetin acted as plasticizer.Composite showed the storage modulus decrease because the plasticizer can lead to increasethe molecular mobility of PLA matrix. Consequently, scanning electron micrograph showedthat CMC was well distributed in PLA matrix. It can be explained that triacetin also acted ascompatibilizer to improve the surface adhesion. Significant enhancement of compositeproperties can be used as candidate material for packaging application.

Figure 1 Tan delta of neat PLA and CMC/PLA composites.

References:1. E. Sykacek, M. Hrabalova, H. Frech, N. Mundigler. Compos. Part A, 40, 1272 (2009).2. L. Suryanegara, A.N. Nakagaito, H. Yano. Compos. Sci. Technol., 69, 1187 (2009)3. D. Briassoulis. J. Polym. Environ, 12, 2, (2004).


B-4

Development of Biodegradable Nanofibers fromPoly-L-lactic Acid and Starch Blend by Electrospinning

Jackapon Sunthornvarabhas1, Pathama Chatakanonda2, Kuakoon Piyachomkwan1,Klanarong Sriroth2,3

1 Cassava and Starch Technology Research Unit, National Center for Genetic Engineering andBiotechnology, Bangkok, Thailand

2 Kasetsart Agricultural and Agro-Industrial Product Improvement Institute, Kasetsart University,Bangkok, Thailand

3 Department of Biotechnology, Kasetsart University, Bangkok, Thailand

Electrospun composite fibers between cassava starch and poly-L-lactic acid havebeen fabricated by single step electrospinning process for biomedical application. Sheet ofcomposite nanofibers of average diameter between 200 nanometer to 2 micron weresubjected to physical, chemical, and biological test to ensure fiber compatibility of variousaspects. Workable ranges of starch solid content within 5-40% have been achieved


B-5

Structure and Properties of Multi-Phase Poly (lactic acid)Blends in the Presence of Antioxidant

Piyawan Pukpanta, and Kalyanee Sirisinha1

Department of Chemistry, Faculty of Science, Mahidol University, Phuttamonthon 4 Road, Salaya,Nakhon Pathom 73170, Thailand (E-mail: [email protected])

Poly (lactic acid) (PLA), with its high strength and modulus, is an interestingbiopolymer to be used as a substitution of petroleum-based material. However, PLA is easilythermal-degraded during melt processing via unzipping and chain-scission reactions, leading toa loss of molecular weight [1]. Antioxidants are generally added to inhibit the moleculardegradation and improve the mechanical properties of polymers [2]. In this study, the effectsof antioxidant on the morphology, thermal, and mechanical properties of PLA-based blendswere investigated. The blends of PLA and poly (butylene adipate-co-terephthalate) (PBAT)and PLA composites containing PBAT and clay were focused on.

SEM analysis revealed a co-continuous structure of the PLA/PBAT (50/50) blend.The structure remained unchanged after the addition of antioxidant. The addition of hinderedphenol antioxidant led to a significant improvement in elongation at break and thermal stabilityof the blends. For example, more than 150% increase in the elongation at break and 16oCincrease in the decomposition temperature of the 50/50 blend were found after the addition of0.3% Irganox antioxidant. Stronger effect of antioxidant on the material properties wasobserved in the PLA/PBAT/clay systems.

References:1. Signori F., Coltelli MB., Bronco S. Polym Degrad Stab 2009, 94, 74-82.2. Cerruti P., Santagata G.., Gomez d’Ayala G.., Ambrogi V., Carfagna C., Malinconico M., Persico P. Polym

Degrad Stab 2011, 96, 839-846.


B-6

Synthesis of Poly(lactic acid)/Clay Compositesby in situ Polycondensation

Kulwadee Kaewprapan1, Siriwan Phattanarudee1,2

1 Program of Petrochemistry and Polymer Science, Faculty of Science, Chulalongkorn University,Bangkok, Thailand

2 Department of Imaging and Printing Technology, Faculty of Science, Chulalongkorn University,Bangkok, Thailand

Poly(lactic acid) (PLA) has currently gained increasing interest because of itsnon-toxic degradation and mechanical properties that can be used in many applications, suchas packaging, biomedical, and tissue engineering. Its inherent brittleness and low heatdistortion temperature are however disadvantages that limit its large-scale application.Typically, PLA is synthesized by a direct polycondensation of lactic acid obtained fromfermentation of sugar feed stocks or ring opening polymerization of lactide in which the latterrequires metal catalysts, such as tin, zinc, and lead, producing high molecular weight productwithin a feasible reaction time. Nevertheless, toxicity and residual trace still affect thermalproperty and biocompatibility of PLA. While, the direct process offers an advantage since itcontains practically no impurity. It had been reported that using non-toxic catalysts in the bulkpolycondensation of lactic acid monomer was an alternative route with no toxicity. PLA/layered silicate nanocomposites have prominently offered higher strength, improved thermal,mechanical, gas-barrier, and flame-retardant properties compared with conventionalcomposites. The current research focused on synthesis of poly(lactic acid)/clay composites viain situ polycondensation by using various non-toxic catalysts. Concentrations of catalyst andclay were varied. Effect of the parameters on viscosity average molecular weight and %yield ofthe synthesized PLAs were characterized. Functional groups present in the resultant polymerswere determined by fourier transform infrared spectroscopy. Thermal stability of thenanocomposites was evaluated by thermogravimetric analysis.

References:1. Cheng Y., Deng S., Chen P., Ruan R., Front Chem China 2009, 4:259.2. Sedlarik V., Kucharczyk P., Kasparkova V., Drbohlav J., Salakova A., Saha P., J Appl Polym Sci 2010,

116:1597.3. Ajola M., Enomoto K., Suzuki K., Yamaguchi A., J Environ Polym Degr 1995, 3:225.4. Bai Y., Lei Z., Polym Int 2007, 56:1261.5. Alexadre M., Dubois P., Mater Sci Eng 2000, 28:1.

Acknowledgement:The authors would like to thank the National Innovation Agency (NIA) for funding this

research.


B-7

Poly(lactic acid) – Based Thermoplastic Natural Rubber

Pranee Bunkaew, Natnicha Boonlong, Varaporn Tanrattanakul*

Bioplastic Research Unit, Department of Materials Science and Technology Faculty of Science,Prince of Songkla University, Hadyai, Songkla, Thailand E-mail: [email protected]

Thermoplastic natural rubber (TPNR) is one kind of thermoplastic elastomer (TPE).The advantage of TPE is it behaves as an elastomer and can be processed as a thermoplastic.TPNR is prepared by melt blending between NR and plastic. To obtain the elastomericproperties, polymer blend should contain plastic more than NR. Therefore, dynamicvulcanization of NR has to be applied during melt blending in order to obtain vulcanized NRcausing a phase inversion in the blend. Poly(lactic acid)-based TPNR is a novel material inTPE family and will be called as a bio-thermoplastic elastomer. The benefit of this TPNR isfully biodegradable. PLA is a well-known biodegradable plastic. NR is also biodegraded bymicro-organisms.

PLA NatureWork® 4042D and NR (STR5CV60) in the ratio of 40/60 was meltblended in the Brabender® Mixer 350E internal mixer at 150oC and the rotor speed of 100rpm. Curatives including sulfur, stearic acid, zinc oxide, antioxidant and MBTH were addedafter NR and PLA well mixing. The blend was compression molded at 155oC. Tensileproperties, resilience, hardness, tear strength and tension set were investigated. NRmastication has been applied before blending with PLA. The results are listed in Table 1.Figure 1 shows stress-strain curves of PLA-based TPNR and Figure 2 shows physicalperformance of vulcanized samples after recycling.

Table 1 Mechanical properties of PLA-based TPNR

Figure 1 Stress-strain curve of TPNRs. Figure 2 A sample sheet before recyling (a) and after recycling: (b) NR, (c) TPNR.


B-8

Preparation, Characterization and Properties ofBiodegradable Polymer Blends of Poly(lactic acid)

and Poly(L-lactide-co-caprolactone)

Kanyarat Suthapakti1, Winita Punyodom1, Kanarat Nalampang1 and Robert Molloy1,2

1 Polymer Research Group, Department of Chemistry, Faculty of Science, Chiang Mai University,Chiang Mai, Thailand 50200

2 Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai,Thailand 50200

E-mails: [email protected], [email protected]

Polymer mixtures of poly(lactic acid), PLA, and a poly(L-lactide-co-caprolactone),P(LL-CL), 50:50 mol % copolymer were melt blended in an internal mixer at 165oC for 20mins. The PLA used was a commercial product (NatureWorks, Product Code No. 4042D)whereas the P(LL-CL) copolymer was synthesized via the ring-opening copolymerization ofL-lactide and caprolactone at 120oC for 72 hrs using 0.1 mol % tin(II) octoate as the initiator [1,2].

The PLA, P(LL-CL) and the PLA/P(LL-CL) blends were characterized by acombination of analytical techniques such as proton and carbon-13 nuclear magneticresonance spectrometry (1H, 13C-NMR), gel permeation chromatography (GPC), anddifferential scanning calorimetry (DSC) [3]. From 13C-NMR, the P(LL-CL) copolymer wasfound to have a tapered rather than a completely random monomer sequencing resulting fromthe different LL and CL monomer reactivities [2]. GPC gave number-average molecular weights,M

n, for the PLA and P(LL-CL) of approximately 150,000 and 12,000-28,000 respectively.

The DSC thermograms of the blends indicated that they were semi-crystalline withcompatibility in the amorphous phase.

Hot-pressed films of the polymer blends of thickness 100-250 �m were produced at180oC. At blend compositions of PLA:P(LL-CL) > 70:30 by weight, the films weretransparent but became translucent at < 60:40. Tensile testing of the blended films showed thatan increase in the P(LL-CL) copolymer content increased flexibility but decreased tensilestrength.

References:1. S.J. Huang, Handbook of Biodegradable Polymers: Poly(lactic acid) and Copolyesters, pp. 287-301,

RAPRA Technology Limited, UK (2005)2. K. Nalampang, R. Molloy, W. Punyodom, Polym. Adv. Technol., 18, 3, 240-248 (2007)3. C.E. Carraher, Polymer Chemistry, 7th Edn., pp. 425-481, CRC Press, USA (2008)


B-9

Preparation of Polymer Blends between Poly(L-lactic acid),Poly(butylene-succinate-co-adipate) and Poly(butyleneadipate terephthalat) for Blow Film Industrial Application

Weraporn Pivsa-Art, Sorapong Pavasupree, Narongchai O-Charoen, Ubon Insuan,Paritud Jailak and Sommai Pivsa-ArtDepartment of Chemical and Materials Engineering, Faculty of Engineering Rajamangala University ofTechnology Thanyaburi, Pathumthani, THAILAND 12110

The blends of poly(lactic acid) (PLA), Poly(butylenes succinate-co-adipate)(PBSA)and poly(butylane adipate terepphthalate) (PBAT) were studied with the objectives to appliedfor blown film extrusion method. The polymer blends were prepared using twin-screwextruder. The ratio of PLA and PBSA was fixed at 80/20 by weight and varied the PBATcontent with 10, 20, 30, 40 and 50 wt%. The screw speed was 80 rpm and varied dietemperatures of 220, 200, and 180oC. It was found that the melt flow index (MFI) and tensilestrength of blends decreased while increasing amount of PBAT, whereas the percentage strainshowed contrastive results. The maximum tensile strength and impact strength were reachedwith the blend of 20 wt% of PBAT. Those conditions were used in the blown film extrusionprocess. The morphology investigation using scanning electronic microscopy (SEM) of PLA/PBSA/PBAT blends showed an excellent compatibility between the three polymers.

Keywords: Poly(lactic acid) (PLA), Poly(butylenes succinate-co-adipate) (PBSA),Poly(butylene adipate terephthalate) (PBAT), Polymer blend, Blown film extrusion.

References:1. Huang, S. J. 1985. Encycl Polym Sci Eng 2: Biodegradable polymers. Wiley-Interscience, New York.2. Shu-Ying Gu., Ke Zhang., Jie Ren and Hui Zhan, 2008. Melt rheology of polylactide/

poly(butyleneadipate-co-terephthalate) blends, Journal of Carbohydrate Polymers 74, pp. 79-85.3. Martin, O. and Averous, L. 2001. Poly(lactic acid): Plasticization and properties of biodegradable

multiphase systems. Polymer, 42(14), pp. 6209–6219.4. Fang, Q. and Hanna, M. A. 1999. Rheological properties of amorphous and semicrystalline polylactic

acid polymers. Industrial Crops and Products, 10(1), pp. 47–53.5. Ogata, N. Jimenez, G. Kawai, H. and Ogihara, T. 1997. Structure and thermal/mechanical properties of

poly(L-lactide)-clay blend. Journal Polymer Science, B35(2), pp. 389–396.6. Bhatia A, Gupta R.K., Bhattacharya S.N., Choi H.J. 2007. Compatibility of biodegradable poly(lactic

acid) (PLA) and poly(butylene succinate) (PBS) blends for packaging application. Korea-AustraliaRheol J 19:125–131.


B-10

Study of In situ Crossslink Reaction of EpoxidizedNatural Rubber (ENR) and PLLA-g-GMA Blend

by Moving Die Rheometer

Wilairat Supmak1, Atitsa Petchsuk1*, Pakorn Opaprakasit2*, Wanwipa Siriwatwechakul,Pramuan Tangboriboonrat3

1 National Metal and Materials Technology Center (MTEC), Pathum Thani 12120 Thailand2 School of Bio-Chemical Engineering and Technology, Sirindhorn International Institute of Technology

(SIIT), Thammasat University, Pathum Thani 12121 Thailand3 Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 Thailand

Uncured natural rubber (NR) is sticky, easily deforms when warm, and is brittle whencold. At this state, its elasticity and mechanical properties relatively are poor. However, theseproperties can be considerably improved by crosslinking reaction. Although crosslinkednatural rubber (NR) exhibits good mechanical properties and rubber elasticity, it shows pooroil and solvent resistances due to the non polar nature. To improve these properties, NR hasbeen modified by various methods. Epoxidized natural rubber (ENR) is one of a goodexample of these modifications. Its structure contains both epoxide and unsaturated sites forfurther modification such as crosslinking reaction. In addition, the epoxide groups not onlyprovide reactive sites for functionalization, but also enhance some properties such as oilresistance, low gas permeability, good wet grip, and high damping characteristics. The oilresistance of epoxidized natural rubber (ENR) is due to the polarity of the epoxide group.Although sulfur cured rubber shows superior mechanical properties in terms of tensile strengthand elongation at break, crosslinking reaction by sulfur curing agent give an unpleasant strongsmell during the fabrication process. To avoid this, other materials such as copolymerconstituting readily crosslinkable functional groups such as acrylate group was employed.

In this work, polylactic acid-co-glycidyl methacrylate (PLLA-co-GMA) containingdifferent GMA contents was blend with ENR in various compositions such as 10/90, 30/70and 50/50. The in situ crosslinking reaction of ENR and PLLA-co-GMA blend wasconducted in a Moving Die Rheometer (MDR) according to ASTM D 5289-95. Elastic torquesof ENR and PLLA-co-GMA blend using benzoyl peroxide as an initiator at 120oC wasmonitored as a function of reaction time. Results showed that most of the blends exhibits highermaximum elastic torques (higher stiffness) than that of pure ENR. In addition, Elastic torquesof 50/50 ENR/PLLA-co-GMA blend was higher than that of 70/30 and 90/10. Moreover, theblend of 50/50 ENR/PLLA-co-GMA containing 19.2 mol% of GMA showed the maximumelastic torques indicating that the amount of GMA content plays a significant role onmechanical properties of polymer blend.

Reference:1. L�pez-Manchado MA, Arroyo M, Herrero B, Biagiotti J. Vulcanization kinetics of natural

rubber–organoclay nanocomposites. Journal Apply Polymer Science (89) (2003).


B-11

Preparation of Polymer Blends of Poly(lactic acid) and(Poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate]

(PHBV) for Textile Applications

Sommai Pivsa-Art1, Natee Srisawat2, Narongchai O-Charoen1, Sorapong Pavasupree1 andChurairat Duangduen3

1 Department of Chemical and Materials Engineering, Faculty of Engineering,2 Department of Textile Engineering, Faculty of Engineering,3 Department of Chemistry, Faculty of Science and Technology, Rajamangala University of Technology

Thanyaburi, Pathumthani, THAILAND 12110

The PLA/PHBV blends were prepared using dry blend in the melt spinning method.The ratios of PLA:PHBV were varied with 100:0, 95:5, 90:10, 85:15 and 80:20 wt%. Thetemperatue of single screw extruder was set at 210 to 235oC with screw speed 9 rpm and freefall at draw speed 450, 500 and 550 m/min. The textile fibers were subjected to thermal,morphology and mechanical property evaluation. The results show that the addition of PHBVwas compatible with PLA in the textile fibers ando increased the flexibility of the blends.The ratios of PLA/PHBV at 95/5 and 90/10 was used for the preparation of knitting socks.The Sonic velocity and Tenacity of the fiber was found to be 2.37% and 0.93 CN/den,respectively.

Keywords: Poly(lactic acid), (Poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate](PHBV), Polymer blends, Biodegradable plastics, Melt spining

References:1. Garlotta, D.A. 2002. Literature review of poly(lactic acid). J. Pol. Env., 9 pp.63-84.2. Fang, Q.; Hanna, M.A. 1999. Rheological properties of amorphous and semicrystalline poly(lactic

acid) polymers. Ind. Crop Prod., 10 pp.47-53.3. Long Jiang., Jijun Huang., Jun Qian., Feng Chen., Jinwen Zhang., Michael P. Wolcott and Yawei Zhu.

2008. Study of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/Bamboo Pulp Fiber Composites:Effects of Nucleation Agent and Compatibilizer. J Polym Environ,16 pp.83–93.

4. Chun YS, Kim WN. 2000.Thermal properties of poly(hydroxybutyrate-co-hydroxyvalerate) andpoly(e-caprolactone) blends. Polymer, 41 pp. 2305–2308.


B-12

Polylactic Acid Graft Polyvinyl Acetateas a Compatibilizer for Starch Blending

Suthawan Buchatip*, Thanawadee Leejarkpai and Atitsa PetchsukNational Metal and Materials Technology Center (MTEC) *Corresponding author: [email protected]

Polylactic acid (PLA) is one of the most interesting biodegradable polymers derivingfrom renewable sources. It possesses not only good mechanical properties, highbiodegradability, but also provides a non-toxic degradation product for industrial plasticapplication. However, PLA is an expensive material which limits its uses for disposable items.[1] A possible problem-solving strategy is by blending PLA with inexpensive, readily availableand biodegradable materials. Starch is a good candidate for blending with PLA due to aninexpensive renewable natural biopolymer. Nevertheless, physical and mechanical propertiesof PLA become significantly worse when blended with starch due to the poor compatibilitybetween the two phases. Such an operation therefore requires a compatibilizer to enhance thecompatibility between the two immiscible phases and to improve the mechanical properties ofthe composite. [2, 3]

In this work, polylactic acid-g-polyvinyl acetate (PLLA-g-PVAc) was used as acompatibilizer for 50/50 starch/PLLA blend. PLLA-g-PVAc was prepared by grafting PVAconto PLLA backbone via free radical polymerization in solution process. Various conditionssuch as type and the amount of initiator, monomer concentration, polymerization time andtemperature were studied. Results showed that the highest mol% of PVAc grafting (16 mol%)was achieved by conducting graft copolymerization in toluene at 110oC for 10 h using DCP asan initiator. The preparation of modified starch and PLLA blend was acquired usingmini-extruder or internal mixer at 140-160oC for 15 min in the ternary system. Effects of theamount of the compatibilizer and mol% grafting of PVAc on properties of polymer blend werestudied. Results revealed that tensile strength and tensile modulus of polymer blend with higherPVAc grafting content compatibilizer showed better properties than that of lower PVAcgrafting content compatibilizer.

Keywords: compatibilizer, free radical polymerization, blending

References:1. Pillin, I., Montrelay, N., Bourmaud, A. and Grohens, Y. (2008). Effect of thermo-mechanical cycles on the

physico-chemical properties of poly(lactic acid), Polymer Degradation and Stability, vol.93,December 2007, pp. 321 – 328.

2. Zhang, J.F. and Sun, X. (2004). Mechanical properties of poly(lactic acid)/starch compositescompatibilized by maleic anhydride, Biomacromolecules, vol.5, April 2004, pp.1446 – 1451.

3. Wu, C.S. (2003). Physical properties and biodegradability of maleated-polycaprolactone/ starchcomposite, Polymer Degradation and Stability, vol.80, November 2002, pp.127-134.


B-13

Physical Properties of PLA-Nanocompositefor Packaging Applications

Nantana Jiratumnukul , Tatcha SonjuiResearch Unit of Advanced Ceramic and Polymeric Materials, National Center of Excellence forPetroleum, Petrochemicals and Advanced Materials, Chulalongkorn University, Bangkok, ThailandDepartment of Materials Science, Faculty of Science, Chulalongkorn University Phayathai Road,Phathumwan, Bangkok 10330, Thailand

Nanocomposite polymers have increased interest due to their characteristic, especially inmechanical and thermal properties. The objectives of this research are to prepare variousPLA formulations incorporated with different organoclays and study the feasibility of using theoptimum formulation as a coating film for paper packaging. Physical properties of dried filmswere investigated as a function of the amount of organoclay in the formulation. It was foundthat addition of organoclay did not increase the viscosity of the formulations. The coating filmsshowed good physical properties and high gloss. However, the gloss of coating films slightlydecreased as the amount of organoclay increased.


B-14

Development of Poly(lactic acid) Film Clarity

Raksit Supthanyakul1, Narin Kaabbuathong3, Tuspon Thanpitcha3,Suwabun Chirachanchai1,2,*1 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, Thailand2 Center for Petroleum, Petrochemical, and Advanced Materials, Chulalongkorn University,

Bangkok, Thailand3 PTT Research and Technology Institute, PTT Public Company Limited, Thailand*Corresponding author E-mail: [email protected]

At present, poly(lactic acid) (PLA) is the most potential biodegradable plastic due toits reliable industrial scale production as well as wide range of applications.1 The fact that PLAperforms a slow crystallization as well as high glass transition temperature (T

g) (above room

temperature ~57�C), PLA is transparent but brittle which always obstruct the practical uses.2

Compounding of PLA with other biodegradable resins of which the glass transitiontemperature is below room temperature is known as a way to toughen the materials.3 It isimportant to note that most PLA blends are opaque and result in the loss of attractiveness ofPLA films and packagings.2,4 Currently, we succeeded in developing a bioadditive which clearlyimproves the clarity of PLA based products through a model case study of PLA/PBS blend asshown in Figure 1. The presentation will cover the significant changes in crystallizationphenomena as observed by polarizing microscope.

Figure 1 Appearances of (a) PLA, (b) PLA/PBS, and (c) PLA/PBSwith Bioadditive films under black background.

References:1. Jamshidian, M.; Tehrany, E.A.; Imran, M.; Jacquot, M.; Desobry, S. Compr. Rev. Food. Sci. F. 2010, 9, 552-571.2. Yokohara, T.; Yamaguchi, M. Eur. Polym. J. 2008, 44, 677-685.3. Zhao, P.; Liu, W.; Wu, Q.; Ren, J. J. Nanomater. 2010, doi:10.1155/2010/287082.4. US 2007/0099016 A1 (2007), T. Nakamura, K. Iwazaki, M. Kato, I. Maruyama (invs.)

Acknowledgements:The present work was a co-research work with PTT Research and Technology

Institute, PTT Public Company Limited. One of the authors, R.S. would like to acknowledgethe 90th Anniversary of Chulalongkorn University Fund (RatchadaphiseksomphotEndowment Fund).


B-15

Poly(butylene succinate) Conjugated with Chitosan:A Novel Bioplastics with Function of Metal Complexation

Nutcha Prasertnasung 1, Suwabun Chirachanchai*,1,2

1 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, Thailand2 Center for Petroleum, Petrochemical, and Advanced Materials, Chulalongkorn University, Bangkok, Thailand*Corresponding Author E-mail: [email protected]

Apple snail (Pomacea canaliculata) is one of the major pests spread over the ricefields and orchid farms.1 Copper and copper ion are proven to be an effective snail inhibitorsubstance.2 In the past, we propose an innovative material by coating chitosan on polyethylenefilm and doping the surface with copper ions. The preliminary field test confirmed the applesnail inhibition effectiveness.3 The function of biodegradability, however, is also important if weconsider the practical use of the film. Poly(butylenes succinate) (PBS) is one of the promisingbiodegradable plastics since its thermal and mechanical properties are similar to polyethylene.This present work demonstrates the conjugation reaction of chitosan onto PBS including thestructural characterization.

References:1. Joshi, R. C. Area-Wide Control of Insect Pests, 2007, 257-264.2. Hoang, T. C.; Rovevich, E. C.; Rand, G. M.; Gardinali, P. R.; Frakes, R. A.; Bargar, T. A. Environ Pollut.

2008, 154, 338-347.3. Phongying, S.; Aiba, S.; Chirachanchai, S. Polymer, 2007, 48, 393-400.

Acknowledgements:The authors acknowledge the Center of Innovative Nano-materials, Chulalongkorn

University.


B-16

Development of Enzymatic Treated Raw Granular Starch/PBAT Blends as Biodegradable Materials

Sirirat Thothong1, Kamol Maikrang1, Amnat Jarerat2

1 Program of Materials Science and Engineering, Faculty of Science, Mahidol University, Bangkok10400, Thailand

2 Food Technology Program, Mahidol University, Kanchanaburi Campus, Saiyok, Kanchanaburi,71150, Thailand

Nowaday, development of biodegradable plastics has become increasingly importantto reduce the problem of plastic waste. Polybutylene adipate terephthalate(PBAT) is analiphatic-aromatic biodegradable copolymer. PBAT has been blended with several polymersincluding starch and polybutylene terephthalate. Starch has been used as attractivebiodegradable filler for environmentally friendly plastics. However, native starch has to bemodified in order to be melt-processed as a thermoplastic. It was found that enzymatictreatment can change smooth surface of starch granules to roughness surface. To obtain thestarch granules with roughness surfaces, raw cassava and rice starch were treated withα-amylase and amyloglucosidase in aqueous solution. The result exhibited that the optimumtemperature for treatment of cassava and rice starch by enzyme were 50 and 70oC. The pHfor hydrolytic treatment of cassava and rice starch was 5.0 and 5.5. Many distinct piths andholes formed by the activity of enzymes on the surface of starch granules were observed byscanning electron microscopy. The obtained starch granules with roughness surfaces weremechanically blended with PBAT by using single screw extruder at different ratios. The resultsshowed that the sample of treated starch blends had higher mechanical properties than those ofuntreated sample blends. This may due to the improved miscibility of the roughness surfaceand the PBAT matrix. Tensile strength (MPa) and elongation at break (%) of the blends weregradually decreased when the amount of raw starch was incorporated higher than 10%by weight.

Keywords: cassava starch, rice starch, biodegradable plastic, polybutylene adipate terephthalate

Refefences:1. Brandelero, R. P. H., Yamashita, F. and Grossmann, M. V. E. The effect of surfactant Tween 80 on the

hydrophilicity, water vapor permeation, and the mechanical properties of cassava starch andpoly(butylenes adipate-co-terephthalate) (PBAT) blend films. Carbohydrate Polymers. 2010; vol.82:1102–1109.

2. Matsubara T., Ammar Y. B., Anindyawati T., Yamamoto S., Ito K., Iizuka, M., and Minamiura N.Degradation of raw starch granules by �-amylase purified from culture of Aspergillus awamori KT-11.J. Biochem. Molecular Biol. 2004; vol.37: 422-428

3. Ren J, Fu H, Ren T, Yuan W. Preparation, characterization and properties of binary and ternary blendswith thermoplastic starch, poly(lactic acid) and poly(butylene adipate-co-terephthalate).Carbohydrate Polymers. 2009; 77(3): 576-82.

4. Witt U, M�ller R-J, Deckwer W-D. New biodegradable polyester-copolymers from commoditychemicals with favorable use properties. Journal of Polymers and the Environment. 1995; 3(4): 215-23.


B-17

Studies on Compatibility of Polymer Blends betweenPoly (trimethylene terephthalate) and Polyamide 4

Prepared by Melt Blend Technique

Sommai Pivsa-art and Piyamas SirisangsawangDepartment of Chemical and Materials Engineering, Faculty of Engineering RajamangalaUniversity of Technology Thanyaburi, Pathumthani, THAILAND 12110

Preparation of polymer blends between Poly (trimethylene terephthalate) (PTT)/Polyamide 4 (PA 4) ratio at 50:50, 60:40, 70:30 and 80:20 %wt with Haake rheomix. Theresults indicated that the polymer blends are less viscosity and rapid flow. Mixing of polymerblends are difficult and can’t be compressed by compression mold machine. Another meltblend technique, twins screw extruder was used replace to Haake rheomix. Twins screwextruder was used to prepare PTT /PA 4 at the ratio of 95/5, 90/10, 85/15 and 80/20 %wt.The effect of additive blend (bond fast) 1, 2, 3, 4 and 5 %wt was studied. The thermalproperties of PTT and PA4 by using DSC showed the melting temperatures were 229 and214.oC, respectively. The polymer blends at different ratios with the melting temperature in therange of 214-229oC. The morphological were test with scanning electron microscopy foundthat the ratio of PTT/ PA 4 at 95/5 is the most compatible. The effect of additive will increasedthe compatibility of polymer blends. The quantity of bond fast was not effect on physicalproperties. However, all of polymer blends were still brittle and could not forming part to testthe mechanical properties.

Keywords: Polymer blends, Poly (trimethylene terephthalate), Polyamide 4, Melt blend technique

References:1. Yu, L.; Dean, K. and Li, L. 2006. Polymer blends and composites from renewable resources.

Progress in Polymer Science 31: 576-602.2. Asadinezhad, A.; Yavari, A.; Jafari, S.H., Khonakdar, H.A.; Bohme F. and Hassler, R. Phase morphology

and thermal characteristic of binary blends based on PTT and PA12. Polymer Bulletin 54: 205-213.3. Tachibana, K.; Hashimoto, K.; Yoshikawa, M.; and Okawa, H. 2010. Isolation and characterization of

microorganisms degrading nylon 4 in the compost soil. Polymer degradation and stability 95: 912-917.4. Kawasaki, N.; Nakayama, A.;Yamano, N.; Takeda, S.; Kawata, Y.; Yamamoto, N. and Aiba, S. 2005.

Synthesis, thermal and mechanical properties and biodegradation of branched polyamide 4. Polymer46: 9987–9993.


B-18

Effect of Cassava Starch Foam Blended with NaturalPolymers on Water Resistance and Mechanical Properties

Kaisangsri, N., Kerdchoechuen, O. And Laohakunjit, N.School of Bioresources and Technology, King Mongkut’s University of Technology Thonburi,49 Tientalya Rd., Thakam, Bangkhuntein, Bangkok 10150

Starch has been used to produce starch-based foam because of low cost, low density,non-toxic, renewability and biodegradable. However foams made from starch are brittle andsensitive to water and require further treatments or ingredients to improve their strength andwater resistance. To overcome these weaknesses, other biopolymers are the way to obtainlow cost and compostable material. Thus, the objective of this study is to improve waterresistance and mechanical properties of cassava starch foam (CSF) by adding zein protein,kraft, chitosan and palm oil at 0, 5, 10 and 15% by weight of starch. The additives were mixedwith starch gel prepared by heating 80g of cassava starch with 100 ml distilled water. Foamwas produced by hot mold baking controlled temperature at 200oC for 5 min. Result showedthat water absorption index (WAI) and water solubility index (WSI) of CSF adding with zeinprotein, kraft, chitosan and palm oil were decreased. The lowest values of WAI (2.79) andWSI (2.22) were found in the CSF added with 15% zein protein. Moreover, it was found thatflexural strength was increased with addition 15% zein protein (4.17 N/mm2) and 15% kraft(4.29 N/mm2). On the contrary, addition of palm oil into CSF gave the lowest flexural strength(0.24-0.9 N/mm2) and compressive strength (0.15-0.16 Mpa). In this study, the addition ofzein protein into CSF could improve water resistance and mechanical properties of flexuralstrength and compressive strength. Karft and chitosan blended into CSF gave slightlyimprovement of water resistance. Although CSF blended with palm oil had the greatest waterresistance, mechanical properties was the lowest.

Keywords: water resistance, water absorption index, water solubility index, cassava starch foam


B-19

Production of Carboxymethylcellulose (CMC)from Bleached Bagasses Pulp

Suthaphat Kamthai1,2 and Rathanawan Magaraphan2

1 Divison of Packaging Technology, School of Agro-Industry, Faculty of Agro-Industry,Chiang Mai University, Chiang Mai, Thailand

2 Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, ThailandE-mail: [email protected] and [email protected]

Bagasse is one of the important agricultural-residues from sugarcane farming. It isnon-wood or stalk fiber and has been known as a highly potential cellulose source. This workfocuses on how to use cellulose content available from bagasse pulp to produce thevalue-added cellulose derivative, carboxymethycellulose (CMC). The work involves theconcise investigation for methods to prepare CMC and for its film properties. The cellulosewas alkalized using NaOH at 20-50% at 25oC. Then monochloroacetic acid (MCA) wasadded to the slurry. The results indicated that the alkalization using 30% NaOH gave CMCwith the highest degree of substitution (DS) of 0.69% and good water solubility of 89.75%.The bagasses CMC film showed 56.58 Mpa tensile strength and elongation at break of 2.67%.The investigation revealed that the supplement of polyethyleneglycol (PEG) in bagasses CMCblended film could change the film properties; i.e. the tensile strength decreased but thepercentage of elongation at break raised.

Keyword: Carboxymethylcellulose, Bagasses and Stalk fiber


B-20

Surface Modification of Natural Rubber Latexfrom Medical Surgical Gloves Using DBD Plasma

Treatment for Chitosan Coating

Sakkawet Yorsaenga and Ratana Rujiravanit 1,2

1 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand2 Center for Petroleum, Petrochemicals, and Advanced Materials, Chulalongkorn University,

Bangkok 10330, ThailandE-mail: [email protected]

Although medical surgical gloves have been used to protect the surgeons’ hands frominfection during operations, the bacterial passing from glove perforation during surgery is asevere problem [1]. In this study, chitosan coating on the surfaces of natural rubber latex filmsfrom medical surgical gloves was performed with the aid of dielectric barrier discharge (DBD)plasma treatment in order to reduce the accumulation of bacteria on the surfaces of the latexfilms. Firstly, the latex films were surface-modified with the DBD plasma treatment under airenvironment to enhance the interaction between natural rubber latex and chitosan. From theresults of the water contact angle measurement, X-ray photoelectron spectroscopy (XPS),atomic force microscopy (AFM) and tensile testing, the optimum DBD plasma treatment timewas found to be at 20 s. The plasma-treated latex films were immersed in an aqueous chitosansolution at different chitosan concentrations. The amount of chitosan deposited on the surfacesof the latex films was quantified by the kjeldahl method. The presence of chitosan coating onthe latex films was also examined by the diazo-dye staining, the scanning electron microscopy(SEM), and the FTIR spectroscopy. The antibacterial activities of the chitosan-coated latexfilms were then investigated against Escherichia coli and Staphylococcus aureus. The resultsrevealed that the amount of the chitosan deposited on the surfaces of the latex films as well asthe antibacterial activities of the chitosan-coated latex films increased with increasing of initialconcentration of chitosan solution.

Reference:1. Julian-Camill Harno, Lars-Ivo Partecke, Claus-Dieter Heidecke, Nils-Olaf Hubner, Axel Kramer, Ojan

Assadian (2010). Concentration of bacteria passing through puncture holes in surgical gloves.American Journal of Infection Control, 38, 154-158.


B-21

Preparation of Chitosan-based MicrocapsulesContaining Phlai oil for Multifunctional Properties

Janejila Suwannapeatay1, Chanchai Sirikasemlert2, Sasiprapha Rattanadilok Na Phuket1,*

1 Department of Home Economics, Faculty of Agriculture, Kasetsart University, Thailand.2 Thailand Textile Institute, Thailand.* To whom correspondence should be addressed. E-mail: [email protected]

In recent years, textile manufacturers pay attention on developments of innovativetextile products; such as, aromatherapy, long-lasting fragrances, insect repellents [1], and skinmoisturizers [2] in order to add value to the products. Microencapsulations have beenintroduced to textile industries for durable fragrant finishing because aromatic oils, as volatilematerials from the outer phase, are protected by the wall of microcapsule therefore theirstability are increased [3]. Traditionally, low- or non-biodegradable polymers synthesized fromnon-bioresourceable precursors; such as, phenol-formaldehyde or melamine-formaldehydeare often reported as suitable microcapsule wall. Alternatively, the bioresourceable chitosan isa naturally abundant copolysaccharide which has many attractive properties, especially,biodegradability, bioactivity, non-toxicity, and biocompatibility. In addition, amino groups ofchitosan are reactive groups for chemical modifications and they can react with microbial cellwalls leading to anti-microbial material. Phlai oil is aromatic oil extracted from Phlai, Thaiherbal, and has many outstanding properties, e.g. pain and muscle inflammation relief,mosquito repellent, and anti-bacteria. However, Phlai-oil is easily volatile which is the problemof finishing Phlai oil onto fabrics by pad-dry-cure technique. Thus, the present workchallenges the preparation of chitosan-Phlai oil microcapsules as an alternative material whichmight be practically used in green textiles for long-lasting Phlai-oil and antibacterial properties.Here, the preparation condition via coaservation technique is proposed. The presentation willinclude the study on effects of chitosan concentrations and cross-linking agent on morphologyof product obtained.

Figure 1 SEM micrograph of chitosan-Phlai oil microcapsules.

References:1. Hirech, K., Payan, S., Carnelle, G., Brujes, L., and Legrand, J. (2003). Microencapsulation of an

insecticide by interfacial polymerisation, Powder Technol., 130-324.2. Monllor, P., Bonet, M.A., Cases, F. (2007). Characterization of the behaviour of flavour microcapsules

in cotton fabrics. Eur. Polym. J., 43, 2481.3. Hong, K. and Park, S. (1999). Melamine resin microcapsules containing fragrant oil: synthesis and

characterization. Mater. Chem. Phys., 58,128–31.


B-22

Formulation and Production of Cassava Starch-BasedBiodegradable Material

Roungrong Thongtan1, Pathama Chatakanonda1 and Klanarong Sriroth2

1 Kasetsart Agricultural and Agro-Industrial Product Improvement Institute, Kasetsart University,Bangkok 10900, Thailand

2 Department of Biotechnology, Faculty of Agro-Industry, Kasetsart University, Bangkok 10900, ThailandE-mail: [email protected]

A starch-based biodegradable material was formulated by blending cassava starch,poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT), useful forproducing consumer products in a pilot-scale. Commercial grade of oxidized and pregelatinizedcassava starches were plasticized into thermoplastic starch (TPS) by extrusion with glyceroland small amount of water prior to drying and mixing with PLA and PBAT. Duringplasticization, oxidized starch exhibited the greater throughput rate (1 kg/h for TPS made of30% glycerol and 70% oxidized starch content) when compared to the rate of pregelatinizedstarch due to its lowest peak viscosity. After subsequent melt blending of TPS, PLA andPBAT, the blends of both types of starches achieved homogeneity. Even though the elongationat break and tear strength as a result of blending PBAT and PLA to pregelatinized starch TPSwere superior to the oxidized starch TPS, the destructuration of starch granule in pregelatinizedstarch accelerated its dissolution in water and increased water sorption, which weakened thematerials. The recommended formulation, which was capable to be converted to consumerproducts such as thermoformed packages and molded articles at production rate up to 100kg/h, comprised of 21-28% oxidized cassava starch, 9-12% glycerol, 34.3-40% PLA and25.7-30% PBAT with an addition of maleic anhydride 1 part per hundred of TPS/PLA/PBATtotal weight. The product from this study was recommended to be kept in dry environment atrelative humidity lower than 70%.

Keywords: blend, cassava, poly(butylene adipate-co-terephthalate), poly(lactic acid),pregelatinized starch, oxidized starch, thermoplastic starch, plasticizing

References:1. Thongtan, R. and K. Sriroth. 2012. Physical properties of thermoplastic cassava starches extruded

from commercial modified derivatives in a pilot scale. Appl. Mech. Mater. 117-119: 1007-1013.2. Thongtan, R. and K. Sriroth. 2011. Effect of cassava starch destructuration to mechanical properties

of compostable blends. Adv. Mat. Res. 337: 159-162.3. Jiang, L., M.P. Wolcott and J. Zhang. 2006. Study of biodegradable polylactide/ poly(butylene

adipate-co-terephthalate) blends. Biomacromolecules 7: 199-207.4. Chaudhary, D.S. 2010. Competitive plasticization in ternary plasticized starch biopolymer system.

J. Appl. Polym. Sci. 118: 486-495.5. Martin, O. and L. Av�rous. 2001. Poly(lactic acid): plasticization and properties of biodegradable

multiphase systems. Polymer 42: 6209-6219.


B-23

Self-Organising Nanostructures of Poly(e-caprolactone)Using Sorbitol Derivatives

Supatra Wangsoub1,2, Phutthachat Soison1, Fred J Davis2, Geoffrey R Mitchell2 and Robert H Olley2

1 Department of Chemistry, Naresuan University, Phitsanulok, 65000 Thailand2 Polymer Science Centre, University of Reading, Whiteknights, Reading, RG6 6AF UKE-mail: [email protected], Tel: +66-55-963433

Sorbitol derivatives were synthesized and studies the ability to form gels in a widevariety of solvents. The critical gel concentration may be as low as 0.1% w/w. Transmissionelectron micrograph showed the formation of highly extended nanofibrils which relate to theextremely low levels of solute required for gelation. SEM and TEM of fibril from chloro andbromo substitutes show smaller in diameter than fibril from unsubstituted compound. Electrondiffraction and x-ray diffraction reveal that these highly extended fibrils are crystalline and highanisotropic. Small amount of sorbitol derivatives dispersed in poly(e-caprolactone) provide avery effective self-assembling nanoscale framework. The application of modest shear flowleads to extremely high levels of polymer crystal orientation. During modest shear flow of thepolymer melt, the additive forms highly extended nanoparticles which adopt a preferredalignment with respect to the flow field. On cooling, polymer crystallisation is directed by theseparticles. The para-chloro substitution is considerably more effective at directing the crystalgrowth of poly(e-caprolactone) than the other substituted compounds. The intensity ofequatorial section from the para-choro substituted increases twice compared to the unsubstitutedcompound. In contrast, the meta-chloro substitution shows the low level of preferredorientation compare to the unsubstituted compound. In conclusion, the combination of sorbitolderivatives and shear flow leads to an overall morphology with a high level of PCL crystalorientation. Without the additives the PCL exhibits an isotropic microstructure. This templatingrepresent a novel and powerful approach to effective microstructure control.

Keywords: poly(e-caprolactone), nanofibrils, self-assembling


B-24

Starch/Cellulose Biocomposites Prepared by High-ShearHomogenization/Compression Molding

Saniwan Srithongkham, Lalita Vivitchanont, Siritorn Narkchamnan and Chularat Krongtaew*Department of Chemical Engineering, Faculty of Engineering, Mahidol University25/25 Putthamonthon 4 Road, Salaya, Putthamonthon, Nakorn Pathom 73170 Thailand*E-mail: [email protected]

Rice straw (Oryza sativa Linn.) was subjected to steam treatment in an alkali solutionto solubilize hemicelluloses and lignin seal surrounding the cellulose bundles. After consecutivesteps of physico-chemical treatment, microfibers were fibrillated using high-shear homogenizeryielding cellulose nanofibers with an average diameter of 40 nm. Isolated cellulose fiberscontaining 87%w/w alpha-cellulose. For biocomposites formation, a set of experiments wasperformed to investigate the influence of cellulose nanofibers on mechanical and physicalproperties of biocomposites formed by compression molding technique. It was found thatstarch biocomposites made from 50%w/w cassava starch and 6%w/w glycerol provided agood result on shape stability with relatively high modulus and tensile strength. Adding 30%w/w cellulose nanofibers increased tensile strength and modulus of biocomposites up to 36%.Since more energy is required to degrade polymeric glucose chains of cellulose [1] comparedwith starch and glycerol [2], thermogravimetric analysis (TGA) showed that adding 30%w/wfibers enhanced the decomposition temperature of biocomposites for approximately 10oC.Scanning electron microscope (SEM) images illustrated alignment of cellulose fibers on thesurface of biocomposites.

References:1. Yang, H., R. Yan, et al. (2007). “Characteristics of hemicellulose, cellulose and lignin pyrolysis.” Fuel

86: 1781–1788.2. Garc�a, N. L., L. Ribba, et al. (2009). “Physico-Mechanical Properties of Biodegradable Starch

Nanocomposites.” Macromolecular Materials and Engineering 294: 169–177.


B-25

Physical Properties and Antioxidant Activity ofCassava Starch-Carboxymethyl Cellulose Films

Incorporated with Quercetin and TBHQ

Wirongrong Tongdeesoontorn1*, Lisa J. Mauer2, Sasitorn Wongruong3, Pensiri Sriburi4 andPornchai Rachtanapun5, 6

1 School of Agro-Industry, Mae Fah Luang University, Chiang Rai, 57100 Thailand.2 Department of Food Science, Purdue University, West Lafayette, IN 47907 USA.3 Division of Biotechnology, Faculty of Agro-Industry Chiang Mai University, 50100 Thailand.4 Department of Chemistry, Faculty of Science, Chiang Mai University, 50200 Thailand.5 Division of Packaging Technology, Faculty of Agro-Industry, Chiang Mai University, Chiang Mai,

50100 Thailand.

6 Materials Science Research Center, Faculty of Science, Chiang Mai University, 50200 Thailand.*corresponding author: (E-mail) [email protected]; (Tel) +665-391-6738

In this research, new antioxidant active food packaging materials were developed andevaluated by addition of antioxidants [quercetin and tertiary butylhydroquinone (TBHQ)] intocassava starch-CMC composite films. The effects of quercetin and TBHQ concentrations(0, 50, 100 and 200 mg/200 ml film solution) on the mechanical properties of the compositefilms were examined. Antioxidant addition improved tensile strength but reduced elongation atbreak of the composite film. FT-IR spectra indicated intermolecular interactions betweencassava starch-CMC and antioxidant by shifting of –OH band and carboxylic groups. DSCthermograms confirmed homogeneity of antixidant films. Increasing quercetin and TBHQcontents decreased water solubility the films. Both the total phenolic content and antioxidativeactivity (DPPH scavenging assay) remained in films during the experimental storage time(30 days).


B-26

Emulsion Copolymerization of a Poly(lactic acid)-meth-acrylate Macromonomer with an Alkyl Methacrylate

Kiyoaki Ishimoto1, Maho Arimoto1, Hitomi Ohara1, Shiro Kobayashi1, Yuki Hayata2,Masahiko Ishii2, Koji Morita3, Hirofumi Yamashita3, and Naoya Yabuuchi3

1 Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan (E-mail: [email protected])2 TOYOTA MOTOR CORPORATION, 1, Toyota-cho, Toyota, Aichi 471-8572, Japan3 Nippon Bee Chemical Co., Ltd., 2-14-1, Shodai-Ohtani, Hirakata, Osaka 573-1153, Japan

Nowadays, bio-based polymers have been extensively developed as sustainablematerials that can replace the conventional oil-based materials. Especially, poly(lactic acid)(PLA) has been a representative of the bio-based polymers, because it can be synthesizedfrom lactic acid obtained from renewable resources. It is expected to use PLA as anenvironmentally benign polymeric material in various fields. Properties of PLA can becompared with those of the oil-based polymers which are used as multipurpose materials. Inthis study, to expand application scope of lactic acid polymers, a new miniemulsion of poly(alkylmethacrylate-graft-lactic acid)s has been developed for coatings application. PLA chains areknown to be hydrolyzed. The graft copolymer synthesis was based on a PLA macromonomerhaving a methacryloyl polymerizable group. Therefore, we expect damage of polymerproperties to be reduced due to the PLA chains in the side-chain. From an environmentalviewpoint, it is desirable not to use organic solvents for coatings. We aimed to develop a watersolvent system of PLA-based coating and film forming materials. Copolymerization of amethacrylate-type macromonomer containing PLA chain with n-butyl methacrylate wascarried out in an emulsion using an anion-type surfactant. These polymers can be a novelbio-based coating material.

Figure 1 Synthesis of PBMA-g-PLA.

Keywords: Environmentally Sustainable Polymer, Poly(lactic acid)-methacrylate Macromonomer,Emulsion Copolymerization, Bio-based Coating Material


B-27

Formulation and Optimization of Heat-Moisture TreatedRice Starch-Glycerol-Carrageenan Composite Film

Using Response Surface Methodology

Rungarun Sasanatayart**School of Agro-Industry, Mae Fah Luang University, 333 Moo1 Thasud, Muang, Chiang Rai, 57100, Thailand

The aim of the current study was to formulate and optimize the formulation on the basisof physical and mechanical properties of the composite film. The films were prepared from2.5% w/w heat-moisture treated rice starch with 33.2% amylose as the main film formingagent. The eleven film formulas based on central composite design were employed to studythe effect of two additives, glycerol (10, 20 and 30% starch) and carrageenan (0.5, 1.0 and1.5% starch), on five parameters, moisture content, color (L* and b*), thickness, tensile strengthand elongation. The Response Surface Methodology (RSM) and multiple responseoptimization utilizing the polynomial equation were used to obtain the optimal formulation withminimum moisture content, maximum tensile strength, and maximum elongation. Optimumlevels of glycerol and carrageenan were predicted by superimposition of contour plot of eachresponse by keeping the required values for each response in view. The optimum combinationfound was carrageenan 1.29% starch and glycerol 16.14% starch. The study helped in findingthe optimum formulation of composite film with acceptable mechanical properties.

Keywords: response surface methodology, composite film, heat-moisture treated starch,carrageenan, mechanical properties.

Session: C

Degradation and standard

Poster Presentation


C-1

Comparison of CO2 Emission and Energy Consumptionbetween Polylactic acid (PLA) and High Density

Polyethylene (HDPE): Thailand Case Study

P. Nanthachatchavankul1,4, S. Chiarakorn2, N. Gridsdanurak3, C. K. Permpoonwiwat5

1 The Joint Graduate School of Energy and Environment, King Mongkut’s University of TechnologyThonburi, Bangkok, Thailand

2 Division of Environmental Technology, School of Energy, Environment and Materials, King Mongkut’sUniversity of Technology Thonburi, Bangkok, Thailand, *Corresponding Author: [email protected]

3 Department of Chemical Engineering, Faculty of Engineering, Thammasat University, Pathumthani, Thailand4 Center for Energy Technology and Environment, Ministry of Education, Thailand5 School of Economics and Public Policy, Srinakharinwirot University, 114 Sukhumvit 23, Wattana,

Bangkok, Thailand 10110

Chemical and petrochemical industry emitted around 800 Million tonnes CO2 in 2005

accounted for 16% of global CO2 emission [1].To reduce those emissions, bioplasticsutilizing

renewable resources as their raw materials instead of fossil fuelwould be acompellingalternative. Polylactic acid (PLA) is the commercially availablebioplastic resin in the market forproducing biodegradable plastic products[2]. Recently, Thai government has implementedNational bioplastic roadmap since January 2006 to promote the production of PLA plant inThailand[3]. Therefore, the scenario of PLA production using cassava as raw material possiblytaken place in Thailand will be simulated as the proxy in this research. High densitypolyethylene (HDPE)accounting for 21% of total commodity plastics production in Thailand(as of 2010)was chosen as the representative to be compared with PLA in this research.Although PLA’s raw material originates from renewable sources, its process requires animmense amount ofenergy and electricity produced from fossil fuel resources. From thisreason, the question is whether PLA production truly reduces CO

2 emission comparing to

those of traditional plastics. Thus, the objective of this research is to compare the CO2

emission and energy consumption from the process of PLA and HDPE. The calculations ofCO

2 emission per kg of each product were carried out using IPCC methodology [4]. Then,

the net CO2 emission of both PLA and HDPE can be obtained from their CO

2 emissions, CO

2

avoidance, and CO2 embedded.The results revealed that energy consumption and CO

2 emis-

sion of PLA production were higher than those of HDPE 2.32 and 2.44 times respectively. Incontrast, if the CO

2 avoidance and CO

2 embedded weretaken into account, the net CO

2

emission of HDPE will be higher than those of PLA 25%. However, there will beviable possi-bilities to reduce CO

2 emission from PLA production. For example, if the renewable energy

such as biomass power plant using cassava waste can be integrated to the PLA plant, it wouldhelp significantly reduce the electricity consumption produced from fossil fuel and lower thegreenhouse gas emission accordingly.

References:1. International Energy Agency (IEA), World Energy Outlook, First Edition, 2006, pp 5-102. E. Rudnik, Compostable Polymer Materials, First Edition, Elsevier, 2008, pp 11-183. National Innovation Agency (NIA), National Roadmap for the Development of Bioplastics Industry,

First Edition, 2008, pp 6-104. International Governmental Panel on Climate Change (IPCC), 2006 IPCC Guidelines for National

Greenhouse Gas Inventories, 2006, Vol.2, pp 20-30


C-2

Organic Fertilizer from Bioplastic Compost

Rochana Tangkoonboribun, Suriya Sassanarakkit, Ratana Tantisirivit, Preecha Rungkvaeand Prasit Bumrungsuk

Organic fertilizers are naturally occurring fertilizers (e.g. compost, manure) which havemany advantages such as insoluble nitrogen as a slow-release fertilizer, increase physical andbiological nutrient, mitigating risks of over-fertilization. The organic fertilizer from bioplasticwas composted from cattle manure and added with different types of bioplastics (thickness 15and 25 micron) compared with Polyethylene (thickness 15 micron) and control. Properties oforganic fertilizer after composted in chamber 7 and 10 days were tested corresponding tostandard of Department of Agriculture. After composted done in 31 days only bioplastic wasdecomposed over than 90% while polyethylene was not decomposed. The compostedfertilizer of bioplastic 15 micron with cattle manure contained with maximum plant nutrients(Total Nitrogen, Total Phosphorus and Total Potassium) 4.31% then was bioplastic 25 micronwith cattle manure with plant nutrients 4.25% then were 4.22% and 3.90% in polyethylene andcontrol respectively. The rate of organic fertilizer from bioplastic application was tested in potexperiment on corn growth. The randomized complete block design of 13 treatments with 4replications was laid at green house of Agricultural Technology Department, Thailand Instituteof Scientific and Technological Research, Pathumthani, Thailand. The rates of compostfertilizer compared between control, composted cattle manure, bioplastic 15 micron, bioplastic25 micron and polyethylene 15 micron at the rate of 1562.5, 3125 and 6250 kilogram perhectare. At 90 days after planted corn yield components e.g. fresh weight of stalk and dryweight of stalk were significant different among treatments at 95% confidential. Yield and yieldcomponents of corn were maximum in cattle manure added bioplastic 25 micron compostedrate 6250 kilogram per hectare then cattle manure added bioplastic 15 micron composted rate6250 kilogram per hectare and composted cattle manure rate 6250 kilogram per hectare withdry weight of seed 42.38, 42.23 and 41.68 gram per pot respectively. The minimum yield andyield component of corn was found in cattle manure added polyethylene 15 micron compostedat the rate of 3125 kilogram per hectare which not different with control.

The organic fertilizer from cattle manure and bioplastic added after composted wellcan be a good source of plant nutrients and improve physical soil properties. However, bioplasticorganic fertilizer should be adapting compost muturity property for standard recommendation.

References:1. Department of Agriculture. 2008. Organic fertilizer analysis method. Department of Agriculture,

Ministry of Agriculture and Cooperatives. 49 p.2. Prasad M., P. Simmons and M.J. Maher. Release Characteristics of Organic Fertilizers. ISHS Acta

Horticulturae 644.http://www.actahort.org/members/showpdf?booknrarnr=644_20.3. Wu L., L.Q. Ma and G.A. Martinnez. 2000. Comparison of methods for evaluating stability and maturity

of biosolids compost. Journal of Environmental Quality 29, 424-429.


C-3

Compostability Studies of PLA and PLA/StarchBlends According to ISO 17088

Yosita Rudeekit, Pongsak Siriyota, Parichat Intaraksa, Monchai Tajan,Phasawat Chaiwuttinan and Thanawadee Leejarkpai*National Metal and Materials Technology Center *Corresponding author: [email protected]

As the increasing in research and development on biodegradable plastics, nowadays,biodegradation testing methods have become a need. A requirement for the labeling ofmaterials as compostable plastics in municipal and industrial composting facilities is theevaluation using ISO 17088. This international standard is used to determine plastic productsthat are designed to be recovered through aerobic composting by addressing four methods;namely chemical characterization, ultimate aerobic biodegradation (ISO 14855-1), disintegrationduring biological treatment (ISO 20200), and ecotoxicity test on the quality of the resultingcompost (modified OECD 208). This paper revealed the compostability performance of PLAand PLA/starch blends. The results were evaluated to identify and verify the compostability ofthe materials. The volatile solid values of PLA and PLA/starch blends with 30, 50 and 70 wt%starch contents from chemical characterization method were 99.98%, 99.96%, 99.94% and99.92%, respectively. The ultimate aerobic biodegradation after 180 days of PLA and PLA/starch blends (30, 50 and 70 wt%) was 83.43%, 84.28%, 88.04% and 95.83%, respectively.Under the same testing conditions, the biodegradation of cellulose as a positive referencematerial was 84.89%. This biodegradation testing was valid because the biodegradability ofthe cellulose powder was over 70% after testing for 45 days. For PLA, a lag phase wasobserved during the first 7 days. The lag phase in the biodegradation curve of PLA/starchblends was not observed since the growth of microbial activity starts immediately. After 35days, the biodegradation of all blended materials reached their plateau phases. Moreover, theresults showed that the biodegradations of the blend samples were increased as the starchcontents increased. In the disintegration testing, both PLA and PLA/starch blends showedinitial degradation with distortion and change in color after the first day of testing. It was foundthat all PLA/starch blends were degraded relatively more rapid than PLA itself. The initialdisintegrations of PLA and PLA/starch blends were observed approximately 7 days afterincubation. The Fragmentation of PLA and all PLA/starch samples were observed after testingfor 14 and 11 days, respectively. All blends were completely disintegrated and no residualcould be observed through visual inspection after 23 days of testing. Whereas the whitepowder size < 2mm was observed as residue remained for PLA after testing for 28 days.Furthermore, no PLA residual could be located through visual inspection after 34 days oftesting. In the ecotoxicity test, the rate of seeding germination and plant growth on the resultingcomposts were not less than 90% of that of corresponding blank compost. Furthermore, theconcentrations of the heavy metals; Zn, Cu, Cd, Pb, Cr and As, in all resulting composts,which were obtained after finishing the biodegradability testing, were lower than the limitationof the standard. It can be concluded that all the tested materials in this study were biodegradableand compostable materials as they pass all the requirements of ISO 17088.

Reference:1. ISO 17088. Specifications for compostable plastics (2008)


C-4

Preliminary Poly Lactic Acid Disintegrationand Toxicity Testing

Anchana Pattanasupong*, Jirapan Srithongkul, and Chanchai KahapanaBioscience Department, Thailand Institute of Scientific and Technological Research, TISTR* Corresponding author: [email protected]

Polylactic acid sheet (PLA 2002D; extrusion process, 0.3-0.6 mm thickness) waspreliminary determined disintegration under stimulated composting condition in a laboratoryscale test according to Plastics-Determination of the degree of Disintegration of PlasticMaterials under Stimulated Composting Condition in a Laboratory Scale (ISO 20200:2004).The result showed the disintegration degree of PLA 2002D was more than 90%, which passedISO 2002:2004. Then, the residue toxicity after the end of disintegration process was testedaccording to Terrestrial Plant Test: Seedling Emergence and Seedling growth Test (OECD208:2006). The compost was mixed with soil in ratio 1:1 by volume to be planting material.The result found the percentage of germination rate, stem height, fresh and dry weight ofmonocotyledon (rice; Oryza sativa) was not significantly difference with control. At the timedicotyledon (pak choy; Brassica campertris var. chinensis) had percentage of germinationrate and fresh weight less than control, while the stem higher than control, and the dry weightwas not difference with control.

Keyword: Polylactic acid, Disintegration, ISO 20200:2004, OECD 208:2006


C-5

Life Cycle Environmental Impact Assessment ofPolylactic Acid Production from Cassava

Pomthong Malakul Na Ayudhaya1,2, Seksan Papong1, Pechda Wenunun1, Warunee Likitsupin1,Tassaneewan Chom-in1, Ruethai Trungkavashirakun1, Manit Nithitanakul2 and Ed Sarobol3

1 National Metal and Materials Technology Center, Thailand Science Park, Pathumthani Thailand2 The Petroleum and Petrochemical College, Chulalongkorn University, Patumwan, Bangkok, Thailand3 Department of Agronomy, Faculty of Agriculture, Kasetsart University, Chatujak, Bangkok, Thailand

Currently, plastic wastes are one of the major environmental problems Thailand isfacing as approximately 2.7 million tons of plastic wastes are generated per year. Of this amount,only approximately 0.2 million tons is being recycled, while the rest has been disposed bylandfill and incineration. In this aspect, the use of bio-based biodegradable plastics can helpreduce the plastic waste management problem as well as global warming impact. In Thailand,bioplastic produced from cassava has been considered the most promising alternative toconventional plastics as cassava is an abundant renewable resource of the country. Theobjective of this study is to analyze the environmental performance of polylactic acid (PLA)production in Thailand based on a life cycle approach. The functional unit is set as onekilogram of PLA resin. The system boundary of the study covers all stages in the life cycle ofPLA production, including plantation, harvesting and processing of cassava, transportation,and polymerization process to produce PLA resin. The input-output data including use ofresources (water, chemicals, materials), energy (electricity, fuel), and all emissions arecollected based on the functional unit. The inventory data from all stages above are thencomplied in SimaPro 7.1 to evaluate the environmental impacts of the cassava-based PLAproduction using Eco-indicator 95 method. The life cycle environmental performance of PLAis compared with that of conventional plastic. The results obtained in this study show that thebioplastic presents better environmental performance than petroleum-based plastic in terms ofglobal warming and reduction in dependency on fossil resources. Detailed of the analysis andsuggestions proposed for improving environmental performance of the bioplastic are presentedin the paper.

Keywords: Life Cycle Assessment, Bioplastic, Polylactic Acid, PLA, Cassava


C-6

System Development and Preliminary BiodegradableEvaluation Tests for Bioplastic Industry by ISO 14855-2

Walaiporn Timbuntam1, Sirinthon Pongsomnam1, Wirat Vanichsriratana2, Prakit Sukyai2*

1 Kasetsart Agricultural and Agro-Industrial Product Improvement Institute (KAPI), KasetsartUniversity, Bangkok 10900, Thailand

2 Department of Biotechnology, Faculty of Agro-Industry, Kasetsart University, Bangkok 10900, ThailandE-Mail: [email protected]

The plastic requirements of earth inhabitant are enormous and have environmentimpacts of such consumption. An average person consumes many tons of those materialswhich ultimately disposed as wastes. Therefore, the trend of environmental awarenessincreases the demanding of biodegradable plastic. Presently, the biodegradability test has beenreported in various kinds of standards. However, the biodegradation in aerobic conditionunder controlled composting system is the main focus of this research. As we have known thatmicroorganisms in compost are the key player of biodegradation which differ from country tocountry. Therefore, our own compost was fermented from rice straw together with cowdropping and urea for 60 days. It was found that the properties of compost were acceptablethe requirements of ISO 14855-2. Such that the compost was utilized for testing thebiodegradation of cellulose and polylactic acid powder which operated by MicrobialOxidative Degradation Analyzer (MODA). The compost was designed to control thehumidity, aeration ratio and temperature at 58oC. It was discovered that the percentage ofbiodegradability of cellulose and polylactic acid powder were 80 and 98, respectively after 60days testing. Thus, from this report, we have confirmed that our compost attain the criterion ofstandard requirement.

Keywords: biodegradability, compost, polylactic acid, ISO 14855-2


C-7

Study of the Disintegration Behavior ofPolymers Starch Blend

Pongsak Siriyota, Yosita Rudeekit, Parichat Intaruksa, Phasawat Chaiwutthinan,Monchai Tajan and Thanawadee Leejarkpai*National Metal and Materials Technology Center *Corresponding author: [email protected]

The disintegration during biological treatment is one of the characteristic requirementsto be identifiead as compostable. Polybutylene adipate co-terephthalate (PBAT) is a syntheticaliphatic aromatic copolymer, which was distributed under the trade name as Ecoflex andEnpol. Poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) is a naturally polyesters. They areknown as biodegradable polymers. The aim of this work was to study the disintegration ofthese polymers with and without the starch. The concentration of the starch in the polymerblends was fixed at 50% by weight. The tested materials were cut into pieces with size of 25mm x 25 mm

x 0.5 mm. The aerobic disintegration testing was carried out in the reactors under

constant temperature at 58 + 2 oC for 90 days. The moisture content, mixing and aeration ofthe samples were periodically controlled according to ISO 20200: 2004 through out thetesting period. According to this standard, the sample is considered to have a satisfactorydisintegration testing if more than 90% of its original dry mass pass through a 2.0 mm sieveafter testing for 90 days. The results showed that the color changes and shrinkage of Enpol andEcoflex were observed after testing for 14 and 30 days, respectively. Both samples becamebrittle and started breaking apart after 45 days. After that, the plastic materials were deformed,brittle and broken into coarse pieces. All blended materials showed the change in color andshrinkage faster than the pure polymers. They became more brittle and disappeared quickerthan the pure polymers. The fragmentation of PHBV/starch and PHBV were observed aftertesting for 9 days and 14 days, respectively. Furthermore, PHBV/starch blend was completelybiodegraded and no residual could be observed through visual inspection after testing for 45days. Whereas the completely biodegradation of PHB was observed after testing for 60 days.The surface morphology of all tested materials before and after disintegration testing wasstudied. Before the disintegration testing, all pure polymers exhibited a uniform continuousmatrix with smooth surface. The starch granular was observed throughout the surface of theblended materials. After testing for 90 days, the surface of all samples became rougher andshowed more cavities than that of the original samples. It was found that the number and size ofthe cavities on the surface of starch based materials were bigger than those of pure materials.The percentages of disintegration of Ecoflex, Ecoflex/starch blend, Enpol, Enpol/starch blend,PHBV and PHBV/starch blend were 25.91%, 80.57%, 56.29%, 91.08%, 100% and 100%,respectively. The degree of disintegration of the starch blended materials was higher than thatof the pure polymers. It can be concluded that the starch content facilitates the disintegration ofthe polymers. Enpol/starch blend, PHBV and PHBV/starch blend were passed therequirement of the standard. However, Ecoflex, Ecoflex/starch blend and Enpol would requirea longer testing time at mesophilic incubation.

Reference:1. ISO 20200. Determination of the degree of disintegration of plastic materials under simulated composting

conditions in a laboratory-scale test (2004).


C-8

Determination of the Aerobic Biodegradability ofthe Starch Based Biodegradable Plasticsunder Controlled Composting Conditions

Parichat Intaruksa, Yosita Rudeekit, Pongsak Siriyota, Phasawat Chaiwutthinan,Monchai Tajan and Thanawadee Leejarkpai*National Metal and Materials Technology Center *Corresponding author: [email protected]

In recent years, considerable interest has been focused on biodegradable polymersdue to their obvious environment friendly property. Starch is a naturally occurring biopolymer,inexpensive and renewable source. Therefore, starch based plastics offer a very attractive lowcost for biodegradable materials. Polylactic acid (PLA) and poly(butylene adipate-co-terphthalate) (PBAT) are known as biodegradable polymers. Blending of PLA or PBAT withstarch is a good way to balance the cost-effective issue. In this study, the biodegradationbehaviors of PLA and PBAT, with and without starch were investigated under controlledcomposting conditions according to ISO 14855-1:2004 for 120 days. All samples were cutinto sizes of 2 x 2 x 0.3 mm3 before submitted to the biodegradation testing. The degree ofbiodegradation of PLA, PLA/starch (50:50), PBAT and PBAT/starch (50:50) whencomparing with that of cellulose were 98.64%, 107.67%, 27.27% and 84.34%, respectively.For PLA, a lag phase was observed during the first 14 days of the testing. This result indicatedthat there was no ultimate biodegradation occurred at the beginning of testing period of PLA.The biodegradation phases of PBAT, PBAT/starch and PLA/starch were observed at thebeginning of biodegradation testing. It is interesting to note that there are two steps ofbiodegradation were observed for PLA/starch. These were expected to be the biodegradationof starch at the beginning of the testing and the later was the biodegradation of PLA. It wasobserved that PBAT/starch was biodegraded for 84.34% which was higher than that of PBATwhich was biodegraded for 27.27%. The results indicated that the addition of starch into thepolymers leads to higher biodegradation of the materials. The surface morphologies of testedmaterials were studied using scanning electron microscope (SEM). The SEM micrographsshowed that polymers blending with starch were attached by microorganism quicker thanpolymers without starch. From the observation, the surfaces of PLA and PLA/starch showedmore degraded than PBAT and PBAT/starch. Furthermore, the characterization structures andthermal properties of the tested materials were determined using fourier transform infraredspectroscopy (FT-IR) and thermal gravimetric analysis (TGA). It was obviously found that theresult of SEM, FT-IR and TGA were in good accordance with the biodegradation results.

Reference:1. ISO 14855-1:2004. Determination of ultimate aerobic biodegradability of plastic materials under

controlled composting conditions – Method by analysis of evolved carbon dioxide., Aamar A.S.,Fariha H., Abdul H. and Safia A. Biotechnogy Advances 26 (2008).p.246-265., Jie R., Hongye F., TianbinR., and Weizhong Y. Carbohydrate Polymers 77 (2009) p.576–582.

Session: D

General

Poster Presentation


D-1

Stimulation of Advanced Technology Research andDevelopment for Thailand Bioplastics Community

Assoc.Prof. Klanarong Sriroth, Uraiwan Dilokkunanant, Suphannij Polasen,Sittipat PetchawatKasetsart University, Bangkok 10900, Thailand

A project management on bioplastic research and development was operated underthe support of the National Innovation Agency (NIA) and Kasetsart University, fromSeptember 1, 2009 to June 30, 2011. The project was run by committees, which includedAdministrative Committee and Monitoring-Evaluation Committee. The committees comprisedof experts from research institutes and representatives from industries and NIA. Mainobjective of the project was to support and accelerate local researchers and scientists todevelop advanced technology and innovation which could help strengthen Thai bioplasticsindustries in the future.

After calling for research proposals, evaluations and allocations, 37 research projectswere funded. The projects were divided into 5 groups: 4 projects for Group A (a group foradvance research on PDLA productions at upstream and middle stream technology), 6 projectsfor Group B (a group for PLA productions at upstream and middle stream technologyincluding optimization), 18 projects for Group C (a group for formulating, molding andcompounding technology), 6 projects for Group D (a group for Life Cycle Assessment) and 3projects for Group E (a group for non-PLA technology). And by the end of June 2011, 15projects were accomplished with 8 patents, 7 papers in international journals and 4 products.At present, there are 22 more projects that are still operating and the last project is expectedto finish by February 2012.

Moreover, the management project had also analyzed bioplastic patents in 2009-2010to foresee research directions. The investigation revealed that, Japan and United States ofAmerica are leaders in research and development on PLA compounding, especially onimproving of mechanical properties, heat tolerant properties and permeability. However, thereare others interesting patents on PLA for various products such as, drug control release,implant device, nanoparticles, nonwoven nanofibers, adhesive material, coating material andso on. For butylenes succinate (PBS), improvements were done for particular products, e.g.anti-permeability, increase permeability, emulsion, drug control release, etc.

As internet is an important mean for sharing information, a database website, http://www.bioplasticthailand.com, was created. In the website, various data related to bioplastics,e.g., Thai researchers, research papers, journals, bioplastic laboratories and institutes, bioplasticindustries and patents, were included.

Documents

The Third Thai-Japan Bioplastics and Biobased Materials ... · PDF fileDibutyl 2,5-Furandicarboxylate ... Novamont/Thantawan Industry PLC 12:30 Lunch. ... Apichai Sawisit Suranaree