pla+phb blend composite

The Second Thai-Japan Bioplastics andBiobased Materials Symposium

(AIST - NIA Joint Symposium)

10 September 2010

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

National Innovation Agency (NIA, Thailand)Kasetsart University (KU, Thailand)

Supported by[JENESYS Program 2010]

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

National Innovation Agency (NIA, Thailand)

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

(biomass) and biodegradable plastics should be the critical materials in 21st century. The purposeof this symposium is to overview the current research activities and global tends on bioplastics(biobased and biodegradable plastics) and biobased materials and to promote these activities inboth countries. In addition researcher exchange between Thailand and Japan will 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

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Contents

Poster Presentation Abstracts

Session A: Fermentation and Monomer Production ............................................................. 17

Session B: Midstream and Intermediate Production ............................................................ 19

Session C: Processing and Application................................................................................. 25

Session D: Degradation and standards ................................................................................. 55

Powerpoint Presentations

I-1 Overview of AISTDr. Seichi Aiba ............................................................................................................... 63

I-2 New Pretreatment System of Biomass and Hyperthermophilic CellulasesDr. Kazuhiko Ishikawa .................................................................................................. 65

I-3 Prospect of Biochemical Conversion of Agricultural Wastes to Sugarsand Value-add ProductsDr. Kazuhiko Ishikawa .................................................................................................. 79

I-4 Microbial Production of Glyceric and from Raw Glycerol and itsApplication to BioplasticsDr. Tokuma Fukuoka ..................................................................................................... 95

I-5 Fully Biomass-based Poly (Butylenes Succinate) Synthesized from Furfuraland its Certification by Accelerated Mass SpectrometryDr. Masao Kunioka ..................................................................................................... 107

I-6 Production of Propylene from Bio-ethanolDr. Tadahiro Fujitani ...................................................................................................... 121

I-7 Processing of Bio-based Polyesters into High-performance fibersProf. Hideki Yamane .................................................................................................... 133

I-8 Optimization of Lactic Acid Fermentation from Local Raw MaterialsUsing a Highly Effective Bacterial StrainDr. Sureelak Rodtong .................................................................................................. 153

I-9 Lactide Synthesis and Polymerization Using Novel CatalystAssoc. Prof. Dr. Winita Punyodom ............................................................................. 167

I-10 Bio-Succinate: Metabolic Engineering Approach for its SustainableProduction in ThailandDr. Kaemwich Jantama ................................................................................................ 183

No. Ref. No Title Aurthor Organization

Session A: Fermentation and Monomer Production

1. A-1 Production of Poly-beta-hydroxybutyrate Kanjana Viwatrungruangdee Silpakorn University(PHB) by a Novel Thermophilic BacteriaDactylosporangium sp. M2.2

2. A-2 Metabolic Flux Analysis of Metabolic Kaemwich Jantama Suranaree University ofEngineered Escherichia coli that Produced TechnologySuccinate during Anaerobic Fermentation

3. A-3 Production of Succinate From Microbial Maytawadee Saengproo Suranaree University ofAnaerobic Fermentation Technology

4. A-4 Production of Poly-β-Hydroxybutyrate by Vichai Leelavatcharamas Khon Kaen UniversityRalstonia solanacearum RS 20 in Batch Culture

5. A-5 High Cell Density Cultivation of Cupriavidus sp. Pensri Plangklang Khon Kaen UniversityKKU38 for Polyhydroxybutyrate (PHB)Production from Cassava Starch Hydrolysate

6. A-6 An Economical D-Lactic Acid Production from Walaiporn Timbuntam Kasetsart UniversityVarious Substrates in Sugar Manufacturing Process

7. A-7 The Production of Polyhydroxybutyrate from Suphat Chomjhai King Mongkut’s Universitya Newly Bacterial Isolate, Strain I-14 of Technology North Bangkok

8. A-8 Purification of D-(-)-Lactic Acid from Apichat Boontawan Suranaree University ofFermentation Broth Using Esterification, TechnologyDistillation and Hydrolysis Technique

9. A-9 Conversion of Glycerol into Kanokporn Sompornpailin King Mongkut’s Institute ofPolyhydroxyalkanoates (PHAs) Using Technology LadkrabangBacterial Metabolism

10. A-10 Potential Bacterial Strains for D-Lactic Acid Sureelak Rodtong Suranaree University ofProduction from Tapioca Starch Technology

Session B: Midstream and Intermediate Production

11. B-1 Synthesis and Characterization of Polylactide- Chantiga Choochottiros Inha UniversityPoly(methyl methacrylate) Copolymer byCombining of ROP and AGET ATRP

12. B-2 Synthesis and Characterization of tin(II) Khamphee Phomphrai Mahidol UniversityComplexes Derived from 9-BBN for thePolymerization of Cyclic Esters

13. B-3 Route to High Molecular Weight of Poly Bongkoch Nonthaboonlert National Metal and Materials(lactic acid) by Solid State Polymerization Technology Center

14. B-4 Synthesis and Crosslinking ofLactide (LA)/ Wilairat Supmak National Metal and MaterialsGlycidyl Methacrylate (GMA) Copolymers Technology Center

Session C: Processing and Applications

15. C-1 The Development of Mulch Film from Tarinee Nampitch Kasetsart UniversityNatural Rubber and Poly (lactic acid)

16. C-2 Preparation and Characterizations of PLA Krisana Siralertmukul Chulalongkorn UniversityComposite Loaded Hydrophobic Chitosan:Melt Mixing and Solution Mixing

The Second Thai-Japan Bioplastics andBiobased Materials Symposium

Poster Presentations

AIST - NIA Joint Symposium 5


17. C-3 Bio-packaging Film from Poly (lactic acid) Piyawan Pukpanta Mahidol UniversityBlends and Composites

18. C-4 Green Composite Film of Polylactic Acid and Duangdao Aht-Ong Chulalongkorn UniversityMicrocrystalline Cellulose

19. C-5 Mechanical Properties of Polylactic acid/ Arpaporn Teamsinsungvon Suranaree University ofPoly(butylenes adipate-co-terephthalate)/ TechnologyCalcium Carbonate Composites

20. C-6 The Study of Using Glycidyl Methacrylate Punmanee Juntuek Suranaree University ofGrafted Natural Rubber as an Impact Modifier Technologyof Polylactic Acid

21. C-7 Effect of Antioxidant Contents on Water Wirongrong Tongdeesoontorn Chiang Mai UniversityVapor Transmission Rate and SorptionIsotherm of Cassava Starch-CarboxymethylCellulose (CMC) Films

22. C-8 Electrospun Nanofibrous Tissue Scaffold Jackapon Sunthornvarabhas National Center for GeneticEngineering and Biotechnology

23. C-9 Toughness Improvement by Blending Chutamas Maneewong Kasetsart UniversityPolyhydroxybutyrate-co-hydroxyvaleratewith Natural Rubber (Hevea brasiliensis)

24. C-10 Properties and Processing of Glutinous Rice Napawan Kositruangchai Chiang Mai UniversityStarch Foam Added Natural Fiber

25. C-11 Effect of Particle Size on Mechanical Properties Roungrong Thongtan Kasetsart Universityof Biobased Composite from Oil Palm Waste

26. C-12 Effect of Corn Husk and Rice Straw Pulp Suphat Kamthai Chiang Mai UniversityMixing Ratio on Carboxymethylcellulose(CMC) Film Properties

27. C-13 Development of Rice Straw Jurmkwan Sungsuwan Chiang Mai UniversityCarboxymethylcellulose (CMC) Film Propertiesfor Anti-anthracnose Fungi in Economic Fruits

28. C-14 Preparation of Polylactide/Organoclay Siriwan Phattanarudee Chulalongkorn UniversityNanocomposite Latexes

29. C-15 Fabrication and Characterization of Sirisart Ouajai King Mongkut’s UniversityMelt Spun Poly(lactic acid) Fiber of Technology North Bangkok

30. C-16 Poly(lactic acid) Composite Film for Coatings Nantana Jiratumnukul Chulalongkorn University

31. C-17 Natural Coloration of Poly(lactic acid) by Prapaporn Ngenkrathok Silpakorn UniversityNatural Dyed Aluminium Silicate Powder

32. C-18 Eco-friendly Binder System for Powder Nutthita Chuankrerkkul Chulalongkorn UniversityInjection Moulding

33. C-19 Fabrication of Stearyl-Chitosan Nanoparticle by Thitirat Rattanawongwiboon Kasetsart UniversityNanoscale Radiation Induction: An Approach forGreen Bio-based Additive for Polylactic Acid

34. C-20 Thermoplastic Starch-based Materials for Nattaporn Khanoonkon Kasetsart UniversityPackaging: Preparation and Compounding

35. C-21 Thermoplastic Starch-based Material for Sarekha Woranuch Kasetsart UniversityFlexible Packaging

36. C-22 Thermoplastic Starch-based Materials for Sumana Kunathan Kasetsart UniversityRigid Packaging

37. C-23 Preparation of Poly(lactide)-β-Poly(butadiene)- Na-Youn Kim Inha Universityβ -Poly(lactide) for PLA Impact Modifiers

The Second Thai-Japan Bioplastics and Biobased Materials Symposium6


38. C-24 Effects of MA-g-PLA compatibilizer on Sutawan Buchatip National Metal and MaterialsPLLA/Starch Blending Technology Center

39. C-25 Morphology and Properties of Polylactic Acid/ Natphichon Budtri Suranaree University ofThermoplastic Starch Blends Technology

40. C-26 Mechanical, Thermal and Rheological Kwan-ho Seo Kyungpook NationalProperties of Modified Poly lactic acid University

41. C-27 Enhancement of Miscibility between Piyawanee Jariyasakoolroj Chulalongkorn UniversityPoly (lactic acid) and Starch SurfaceModified with Silane Coupling Agents

42. C-28 Conjugating Starch on Poly(butylene succinate): Kanitporn Suchao-in Chulalongkorn UniversityA Simple Approach to Prepare PBS Masterbatch

Session D: Degradation and Standards

43. D-1 Biodegradability test of PLA-based Composites Napakarn Kawee Kasetsart Universityby ISO 14855-2

44. D-2 A Comparison of Life Cycle Environmental Unchalee Suwanmanee Kasetsart UniversityImpact of Polylactic Acid and Polystyrene Trays

45. D-3 Application of Life Cycle Assessment Pomthong Malakul National Metal and MaterialsTechnique to Polylactic Acid (PLA) and Technology Centerits Products Produced in Thailand

46. D-4 Biodegradation of PLA and PLA/Starch Blends in Yosita Rudeekit National Metal and MaterialsLandfill and Controlled Composting Conditions Technology Center

47. D-5 Determination of the Aerobic Biodegradability Pongsak Siriyota National Metal and Materialsof Polylactic Acid and Starch Co-Extruded Technology CenterMaterial in an Aqueous Medium

48. D-6 Control of Biodegradability of Poly(butylene Yuya Tachibana National Institute of Advancedsuccinate) by Addition of Cellulose Acetate Industrial Science andButyrate Technology

49. D-7 Biomass Carbon Ratio of Polymer Products Masahiro Funabashi National Institute of AdvancedMeasured by Accelerator Mass Spectrometry Industrial Science and

Technology

Session: A

Fermentation and Monomer Production

A-1

Production of Poly-beta-hydroxybutyrate (PHB) by a Novel Thermophilic Bacteria Dactylosporangium sp. M2.2

Kanjana Viwatrungruangdee1, Sathita Phol-in1, Witsanu Srila1, Tippaporn Sophonpattanakit1, Adisak Jaturapiree1, and Phimchanok Jaturapiree1,*

1 Department of Biotechnology, Faculty of Engineering and Industrial Technology, Silpakorn University, Muang, Nakhon Pathom 73000 Thailand (E-mail: [email protected])

2 Faculty of Industrial Technology, Phranakhon Rajabhat University, Bangkhen, Bangkok 10220 Thailand

Abstract

A short rod-shaped and gram-positive bacterium (designated strain M2.2) able to accumulate PHB was isolated from soil samples at Maekhachan hot spring, Chiang Rai province, Thailand. The partial nucleotide sequence 16S rDNA indicated that the strain M2.2 showed a high similarity to Dactylosporangium sp. The effects of selected carbon sources: glucose, lactose, glycerol, butyric acid and acetic acid on the production of PHB were determined. It was found that the optimum medium for PHB production of M2.2 consisted of glycerol (0.2%), lactose (1.0%) and glucose (3.0%) with PHB concentrations of 42.81, 11.20 and 1.57 mg/l, respectively. The bacterium M2.2 could not grow or accumulate PHB when using butyric acid or acetic acid as sole carbon source.

Keywords: PHB, Carbon source, Thermophilic bacteria, Dactylosporangium sp.

A-2

Metabolic Flux Analysis of Metabolic Engineered Escherichia coli that Produced Succinate during Anaerobic Fermentation

Kaemwich Jantama1, Spyros A. Svoronos2, and Lonnie O. Ingram3

1 School of Biotechnology, Institute of Agricultural Technology, Suranaree University of Technology, Nakhon Ratchasima, Thailand 30000 ([email protected])

2 Department of Chemical Engineering, University of Florida, Gainesville, FL 32611 USA 3 Department of Microbiology and Cell Science, University of Florida, Gainesville, FL 32611

USA

Abstract

Metabolic flux analysis (MFA) was performed to assess the distribution of intracellular metabolites during anaerobic metabolism of Escherichia coli strains when glucose concentration was varied. Batch experiments were conducted with a wild type of E. coli and four succinate-producing strains constructed previously in order to establish how metabolic fluxes changed as a result of gene deletions and metabolic evolution. The flux through pyruvate dehydrogenase (PDH) complex was added to the classical anaerobic fermentation pathways, and mutants lacking pyruvate formate-lyase (PFLB) increased the flux through this pathway to produce NADH required for succinate production. Also, the mutants utilized phosphoenolpyruvate synthase (PPS) to convert pyruvate produced during glucose phosphorylation back to phosphoenolpyruvate (PEP). This provided additional PEP utilized for producing succinate. Three mutants had pflB deleted, and these exhibited considerably higher flux to oxaloacetate (OAA). Increased glucose concentration did not affect the fluxes significantly, other than decreasing lactate production for the wild type from low to lower levels and decreasing the flux to biomass for the mutant strains. ATP generation was also studied. The wild type and a pflB+ mutant had ATP yield close to the maximum theoretical values. However, the pflB- mutants had very low ATP yield. It is hypothesized that the strains may activate some unknown ATP generating pathways.

Keywords: MFA, Escherichia coli, Succinate, PDH

A-3

Production of Succinate From Microbial Anaerobic Fermentation

Maytawadee Saengproo, Sitha Chan, and Kaemwich Jantama

School of Biotechnology, Institute of Agricultural Technology, Suranaree University of Technology, Nakhon Ratchasima, Thailand 30000 ([email protected])

Abstract

Succinate is an intermediate produced in the metabolic pathway of several anaerobic and facultative microorganisms. Many bacteria have a natural ability to produce succinate as a major fermentation product. Rumen bacteria such as Actinobacillus succinogenes, Anaerobiospirillum succiniciproducens and Mannheimia succinoproducens can produce at high rates (up to 4 g/l-h) with impressive titers of succinate (300-900 mM) and high yields (>1.1 mol succinate/glucose). Electrodialysis, sparging with CO2, cell recycle, and batch feeding were combined. However, these natural producers require complex media, which add cost associated with production, purification, and waste disposal. Since E. coliexhibits fast growth, is able to grow in the minimal medium, and many genetic techniques can be applied, it is a target microorganism to be developed for practical succinate production. In the past decade, many groups have been studying extensively to obtain high production yield of succinate by metabolic engineering of E. colistrains. The native genes of central anaerobic metabolism were eliminated from chromosomal DNA of E. coli. To obtain high succinic acid yield, the carbon flux through the phosphoenolpyruvate carboxylation route should be active rather than that through pyruvate. Other genes involved in producing organic acids other than succinate should be inactivated then the strain channels the phosphoenolpyruvate to succinate.

Keywords: Metabolic engineering, Rumen bacteria, Fermentation, Succinate

A-4

Production of Poly-�-Hydroxybutyrate by Ralstonia solanacearum RS 20 in Batch Culture

Vichai Leelavatcharamas1, Jantima Teeka2, Vanla Dittapongpitch3and Sanha Panichajakul2

1 Fermentation Research Center for Value Added Agricultural Products (FerVAAP), Faculty of Technology, Khon Kaen University, Khon Kaen, Thailand

2 Department of Biotechnology, Faculty of Technology, Khon Kaen University, Khon Kaen, Thailand

3 Department of Plant Pathology, Faculty of Agriculture, Khon Kaen University, Khon Kaen, Thailand

Abstract

Among 70 isolates of Ralstonia solonacearum, R. solonacearum RS20 exhibited the highest poly-�-hydroxybutyrate (PHB) accumulation. Optimum conditions for PHB production of R. solonacearum RS20 in shaking flask were studied. R. solonacearum RS20 showed the highest amount of polyester when cultured at 30 �C, pH 7 and shaking speed of 300 rpm. Among 6 carbon sources, glucose was the suitable carbon source for the polyester production. The optimum C/N ratio in mineral medium for PHB production was 1 g/l ammonium hydrogen phosphate per 40 g/l glucose. Effects of carboxylic acid, which were butyric acid, propionic acid and valeric acid, on growth and co-polyester accumulation of R. solonacearum RS20 were also examined. It was found that only 3 Hydroxybutyrate monomer was obtained. Thus, it was possible that R. solonacearum RS20 could not utilize propionic acid and valeric acid as precursor for co-polyester production.

Keywords: Poly-�-Hydroxybutyrate, co-polyester, Ralstonia solanacearum

A-5

High Cell Density Cultivation of Cupriavidus sp. KKU38 for Polyhydroxybutyrate (PHB) Production

from Cassava Starch Hydrolysate

Pensri Plangklang1, Mullika Teerakul1, Mallika Boonme1 and Alissara Reungsang1,2*

1 Department of Biotechnology, Khon Kaen University, Khon Kaen 40002 Thailand 2 Fermentation Research Center for Value Added Agricultural Products, Khon Kaen

University, Khon Kaen 40002, Thailand * Correspondence author: E-mail: [email protected]

Abstract

This study investigated the high cell density cultivation of Cupriavidus sp.KKU38 for polyhydroxybutyrate (PHB) production from cassava starch hydrolysatein fed-batch and repeated fed-batch mode. The fed-batch experiment with the exponential feeding mode was conducted. The high cell density of 74 g/L and the PHB productivities of 1.81 g/L.h were obtained with the PHB content of 64%. The PHB production in repeated-fed-batch was further investigated under phosphorus-limited condition. The pulse followed by exponential feeding was conducted in each repeated feeding period to provide the optimal condition for both biomass production and PHB accumulation of KKU38. The results indicated that the high cell density of 110 g/L could be obtained with the biomass and PHB productivities of 2.94 and 2.16 g/L.h, respectively. The biomass and PHB yields of 0.34 g-cell/g-sugar consumed and 0.25-g PHB/g-sugar consumed with the PHB content of 74% were achieved. However, the growth rate of KKU38 was found to decrease when the high cell density was achieved. The product inhibition and/or the decrease in the dissolved oxygen level in the culture broth might cause these effects.

Keywords: Polyhydroxyalkanoates, Cupriavidus KKU38, Cassava starch, Fed-batch

A-6

An Economical D-Lactic Acid Production from Various Substrates in Sugar Manufacturing Process

Walaiporn Timbuntam1, Yutaka Tokiwa2, Pipat Weerathaworn3 and Klanarong Sriroth1,*

1 Department of Biotechnology, Faculty of Agro-Industry, Kasetsart University, Bangkok, Thailand

2 National Institute of Advanced Industrial Science and Technology (AIST),Tsukuba Central 6, 1-1-1 Higashi, Tsukuba, Ibaraki, Japan

3 Mitr Phol Sugarcane Research Centre, Phukieo, Chaiyaphum, Thailand * Author for correspondence (Fax: 662-940-5634; E-mail: [email protected])

Abstract

Poly (lactic acid) (PLA), a kind of biodegradable polymer, is a potential environmentally friendly substitution of non-biodegradable plastics derived from petrochemicals. Recently, D-lactic acid has the potential to improve the mechanical and thermal characteristics of PLA by the equimolar blend of Poly (L-lactic acid) (PLLA) and Poly (D-lactic acid) (PDLA) called stereocomplex. Nevertheless, the D-lactic acid is still more expensive because of limitation of producer and high production cost. To reduce the cost, the inexpensive raw materials from the sugar manufacturing process such as refined sugar, raw sugar, primary juice, mixed juice, clarified juice, raw syrup and molasses, were demonstrated for the production of D-lactic acid in this study. The initial sugar concentration was conducted at 100 g/l which illustrated high sucrose content. The results showed that the well-performing bacteria selection Lactobacillus sp. TOKAMI 9 is efficiency produced D-lactic acid from raw syrup and molasses. The D-lactic acid production, %yield and productivity of raw syrup are 96 g/l, 88.3% and 3.21 g/l.h, respectively. In case of molasses, the 88 g/l of D-lactic acid is produced with the %yield and productivity are 82.1% and 1.83 g/l.h, respectively. It can assume that sugar industry could be a potential producer for economical production of the D-lactic acid from sugarcane raw syrup and molasses at a commercial scale.

A-7

The Production of Polyhydroxybutyrate from a Newly Yeast Isolate, Strain I-14

Suphat Chomchai and Rotsaman Chongcharoen*

Department of Agro-Industrial Technology, Faculty of Applied Science, King Mongkut’s University of Technology, North Bangkok (KMUTNB), Thailand (E-mail: [email protected])

Abstract

A yeast strain I-14, isolated from food industrial wastewater, was tested for the accumulation of polyhydroxybutyrate (PHB) along with known PHB producers, Alcaligenes latus ATCC 29714 and Alcaligenes eutrophus ATCC 17699. From preliminary studies in flask-scale culture, it was found that nitrogen source and rotational speed affected growth and the accumulation of PHB in both A. latus and strain I-14. The cell and PHB concentrations of strain I-14, grown on basal medium (BMM) with 20 g/l of glucose and 2 g/l (NH4)2SO4, were 6.19 and 5.25 g/l, respectively. In addition, the glucose-grown strain I-14 showed greater PHB content of 84.7% (w/w), in comparison to that of glucose-grown A. latus. However, the cell concentration of A. eutrophus, grown under the same condition, increased about 2-fold with relatively low glucose conversion to PHB. Strain I-14 was also grown on 20g/l glucose + maltose (80:20). It was found that the concentration of cell and PHB obtained was 5.98 and 4.05 g/l, respectively, while the percent content of PHB decreased to 78% (w/w), as compared to that obtained from applying glucose alone. When maltodextrin was used as a carbon source, cell concentration of 5.11 g/l was obtained with markedly almost 100% (w/w) PHB accumulation.

Keywords: polyhydroxybutyrate, PHB producer, Alcaligenes latus, Alcaligeneseutrophus, batch culture

A-8

Purification of D-(-)-Lactic Acid from Fermentation Broth Using Esterification, Distillation and Hydrolysis Technique

Apichat Boontawan1, and Weerasak Leartsiriyothin2

1 Biofuel Production from Biomass Research Unit, School of Biotechnology, Institute of Agricultural Technology, (E-mail: [email protected])

2 School of Agricultural Engineering, Institute of Engineering, Suranaree University of Technology, 111 University Avenue, Muang district, Nakhon Ratchasima, Thailand

Abstract

Esterification reactions of D-(-)-lactic acid with anhydrous ethanol were carried out to synthesize ethyl lactate with the objective to purify D-(-)-lactic acid from other impurities. Sulfuric acid was used as the catalyst. Esterification reaction is characterized by thermodynamic limitation on conversion because of the water formation. Consequently, higher esterification yield and volumetric productivity can be obtained by shifting the reaction toward product formation by continuous removal of water. Hybrid processes such as reactive distillation coupling with dehydration processes instead of using only a large excess of anhydrous ethanol is very attractive. In order to increase economic viability of the process, the concept of dual fermentation biorefineries for production and purification of lactic acid was introduced. Cassava was used as the main carbon source for both lactic and ethanol production processes. For D-(-)-lactic acid process, the fermentation broth was evaporated until the water content reduced to approximately 25% prior to start the esterification reaction. In anhydrous ethanol production, the fermentation broth was processed in our laboratory by using a patented distillation column followed by vapor permeation and pressure swing adsorption (PSA). With the combination of these powerful dehydration techniques, the purity of ethanol was increased to as high as 99.99% by weight. In addition, these dehydration units were employed to remove water generated from esterification reactions with the main objective of recycling ethanol back to the esterification process. In comparison, the productivity and conversion yield of esterification reaction were significantly increased when the reaction was coupled with a reactive distillation system. The effect of several process variables such as feed-ethanol ratios, water feed concentrations, and catalyst concentrations on purification performance were investigated. Experimental result revealed that approximately 100% conversion yield was conveniently achieved within 6 hours of operation by repeated addition of anhydrous ethanol accompanied by removal of water by the means of distillation. Subsequently, hydrolysis of ethyl lactate with double distilled water yielded more than 95% optical purity of D-(-)-lactic acid.

Keywords: D-Lactic acid, Ethanol, Esterification, Distillation, Hydrolysis.

A-9

Conversion of Glycerol into Polyhydroxyalkanoates (PHAs) Using Bacterial Metabolism

Kanokporn Sompornpailin 1, 2and Tanapong Kasemsuk1

1 College of KMITL Nanotechnology, King Mongkut’s Institute of Technology Ladkrabang, Bangkok 10520, Thailand (E-mail: [email protected])

2 ThEP Center, CHE, 328 Si Ayutthaya Road, Bangkok 10400

Abstract

Polyhydroxyalkanoates (PHAs) have produced as energy storage macromolecules in many species of bacteria. These natural PHAs are being substituted for petroleum-derived polymers however a fermentation processing for the PHA productions is more expensive. The excess glycerol generated as a byproduct from biodiesel production has become an alternative carbon source. In this experiment, two bacterial strains (Alcaligenes latus and Cuprividus necator) were used in two stage cultures. The fresh cells were collected from A. latus and C. necator cultures used glucose as carbon source at 24 h and transferred into PHA production medium with glycerol or sugars (glucose and sucrose). C. necator shows the better in growth and PHA production in all tested carbon media. Both strains of bacteria cultured in sugar media present the fresh cell production and PHB production rates better than those in glycerol. The characterization of gene involved in glycerol conversion into PHAs and the developments of high potential bacterial strains will be a trend in the reduction cost of PHA production.

Keywords: Polyhydroxyalkanoates, PHAs, Glycerol, Alcaligenes latus, Cuprividus necator

A-10

Potential Bacterial Strains for D-Lactic Acid Production from Tapioca Starch

Sureelak Rodtong, Sudarat Pramkaew, and Aiyara Pananu

School of Microbiology, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima, Thailand (E-mail: [email protected])

Abstract

D-Lactic acid has been of interest to be used in bioplastics industry since it can be used to synthesize poly(D-lactic acid) that can improve the thermostability of poly(L-lactic acid), the main component of biodegradable plastics. Potential microorganisms are still desirable for the production of optically pure D-lactic acid. Two starch-utilizing lactic acid bacterial strains isolated from their habitats in Thailand, could produce D-lactic acid with >99.9% optical purity from tapioca starch, a cheap raw material. Conditions for growth and lactic acid production of the two strains were initially investigated. The suitable medium was found to compose of tapioca starch, tryptone, and spent brewer’s yeast as main ingredients. The two bacterial strains had their specific growth rates (μmax) of 0.89 and 0.93 h-1, when cultivated in 5 L fermentation medium containing 20 and 30 g/L tapioca starch, respectively, in a 6.6 L bioreactor at 35°C. And D-lactic acid yields of 14.56 and 19.76 g/L (YLA/S, of 73.0 and 66.51%), respectively, with >99.9% optical purity were achieved at 48 h of cultivation. Results from this study reveal that these bacterial strains have their potential to directly produce high optical purity of D-lactic acid from tapioca starch.

Keywords: Lactic acid bacteria, D-Lactic acid, Tapioca starch

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Session: B

Midstream and Intermediate Production

B-1

Synthesis and Characterization of Polylactide-Poly(methyl methacrylate) Copolymer

by Combining of ROP and AGET ATRP

Chantiga Choochottiros and In-Joo Chin*

Department of Polymer Science and Engineering, Inha University, Incheon, 402-751, KOREA

Abstract

Polylactide (PLA) is a thermoplastic, high-strength, high-modulus polymer that can be made from annually renewable resources to yield articles for use in either the industrial packaging field or the biocompatible/bioabsorbable medical device market. Conventional method to prepare PLA is ring-opening polymerization by using Sn(II)2-ethylhexanoate (Sn(oct)2) as initiator. Molecular weight of PLA is 9765 g/mol (Pdl 1.69) and 7567 (Pdl 1.18) as determined by GPC. PLA was functionalized with 2-bromoisobutyryl bromide to active PLA chain end as �-bromo carbonyl group, which was used to initiate polymerization of methyl methacrylate (MMA). Atom transfer radical polymerization (ATRP) is one of the most successful control/living radical polymerization (CRP). However, ATRP has some limitations. Since ATRP is initiated by redox reaction between an initiator with a radically transferable atom or group and a catalyst complex comprising a transition metal compound in a lower oxidation state, the transition metal complexes can be easily oxidized to higher oxidation state. An Activator generated by electron transfer for ATRP (AGET ATRP) overcome this limitation by applying Sn(oct)2 to generate in-situ reduction. PLA-PMMA copolymer was succeeded as characterized by 1H NMR, 13C NMR, DSC and TGA.

Keywords: lactide, atom transfer radical polymerization (ATRP), methyl methacrylate (MMA), PLA-PMMA copolymer, impact modifier

B-2

Synthesis and Characterization of tin(II) Complexes Derived from 9-BBN for the Polymerization of Cyclic Esters

Khamphee Phomphrai*,and Parichart Piromjitpong

Center for Catalysis, Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok, Thailand (E-mail: [email protected])

Abstract

Polymers derived from cyclic esters such as lactide, glycolide, and �-caprolactone have received considerable attentions due to their biocompatibility and biodegradability. The polymerizations can be catalyzed using various metal complexes such as Zn, Ca, Mg, Fe, Sn, Al, La, and Ti. Tin(II) 2-ethylhexanoate has been used commercially as a catalyst due to its high solubility and stability in the molten monomers despite the low activity compared to other metal complexes. Thus, a search of more active tin(II) complexes is needed. In this work, a series of bidentate ligands (L) derived from 9-BBN (9-Borabicyclo(3.3.1)nonane) are synthesized. They form complex with tin(II) giving a compound in a general formula L2Sn. These compounds will be tested for catalytic activity in the polymerization of cyclic esters.

Keywords: Tin(II) complexes, Catalyst, Polymerization

B-3

Route to High Molecular Weight of Poly (lactic acid) by Solid State Polymerization

Bongkoch Nonthaboonlert, Atitsa Petchsuk and Kongkiat Kongsuwan

National Metal and Materials Technology Center (MTEC) 114 Thailand Science Park, Paholyothin RD., Klong Luang, Pathumthani, Thailand 12120

Abstract

Generally, PLA can be produced by several methods. Melt polycondensation is the least expensive process to produce PLA. Disadvantage of this method, can only produce low and medium molecular weight product because of the limit of an increased melt viscosity and operating temperature. As a result, solid state polymerization (SSP) is an alternative route to increase molecular weight of poly(lactic acid). This process involves heating solid powder of low and medium molecular weight of poly(lactic acid) to the temperature higher than the glass transition (Tg), but lower than the onset of melting temperature (Tm) so as to make the end groups mobile enough to react and removal by products from the surface of the materials under reduced pressure. The advantages of solid state polymerization, which control over the side reactions as well as thermal, reduce discoloration and degradation of product. Solid state polymers often have improved properties, because monomer cyclisation and other side reactions are limited. There is practically no environment pollution, because no solvent is required. The aim of this research is to increase molecular weight of PLA which produced from melt polycondensation by solid state method. Various molecular weight of PLA, denoted as low (3000, 5000 Da), medium (10000, 15000 Da) and high (25000 Da) were studied. The solid state post polycondenzation was conducted at 170oC for 30 h to obtain a high polymer without discoloration. From GPC result, it revealed that the molecular weight of low, medium and high molecular weight PLA can be increased by 6-7 times, 3-4 times and 1 time respectively. These results could be attributed to higher content of reactive functional end group (-OH and –COOH) of low molecular weight PLA than that of medium and high molecular weight PLA resulting in higher possibilities in connecting polymer chains.

Keywords: Solid state polymerization, High molecular weight PLA, Polylactic acid

B-4

Synthesis and Crosslinking of Lactide (LA)/Glycidyl Methacrylate (GMA) Copolymers

Wilairat Supmak1, Atitsa Petchsuk1*, Pramuan Tangboriboonrat3,Wanwipa Siriwatwechakul2 and Pakorn Opaprakasit2*

1 National Metal and Materials Technology Center (MTEC), Pathum Thani 12120 Thailand 2 School of Bio-Chemical Engineering and Technology, Sirindhorn International Institute of

Technology (SIIT), Thammasat University, Pathum Thani 12121 Thailand 3 Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400 Thailand

Abstract

PLA is biodegradable aliphatic polyester, with high strength and high modulus. However, some of its properties, such as thermal stability, toughness and gas-barrier, are still not satisfactory for various end-use applications. Many approaches were performed to improve these properties, such as stereocomplexation with PDLA to improve thermal properties (melting temperature increased around 50�C), blending with other polymers or inorganic materials to improve mechanical properties, and copolymerization with other polymers to obtain random, block or branch copolymers in order to improve their thermal and mechanical properties.

Copolymerization of lactide with functional comonomers is one of the most interesting approaches, not only to improve their properties, but also to provide functionalities, especially unsaturated groups which can be used as crosslink junction to form thermoset polyester. Glycidyl methacrylate (GMA) is a commercially interesting functional monomer because of the presence dual functionality, containing both epoxy and methacrylic groups. Epoxy is used in a polymerization process and subsequently methacrylic group is intended for a crosslinking process. Therefore, the objective of this study are focused on synthesize functional copolymers of LA and GMA by ring opening polymerization and investigate parameters affecting the crosslinking process of LA/GMA copolymer. The chemical structure and polymer composition were characterized by Nuclear Magnetic Resonance Spectroscopy(NMR). Thermal properties characterized by Differential Scanning Calorimeter (DSC). The molecular weights and molecular weight distribution were determined using a Gel Permeation Chromatography (GPC).

GMA compositions in feed is varies from 2 – 30 mol%. The results from NMR indicate that GMA comonomer is successfully introduced into PLA polymer chain via ring opening polymerization using Sn(Oct)2 catalyst. Properties of copolymer varied from amorphous to semicrystalline polymer with melting temperature in the range of 113-154�C. Crosslinking of the resulting copolymer is then studied by conventional radical reaction using benzoyl peroxide (BPO) as a curing agent. The copolymer with 6.9 mol% GMA is used to study effects of curing parameters, such as crosslinking time and temperature, on % gel content of the cured polyester network. In case of %gel content, it was found that the highest % gel content is obtained when the LA/GMA copolymer is cured at 120�C for 1 h.

Keywords: Lactide, Glycidyl methacrylate, Copolymer, Crosslink process, % Gel content

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54

Session: C

Processing and Applications

C-1

The Development of Mulch Film from Natural Rubber and Poly (lactic acid)

Tarinee Nampitch1* and Rathanawan Magaraphan2

1 Department of Packaging Technology, Faculty of Agro-Industry, Kasetsart University (Email: [email protected])

2 The Petroleum and Petrochemical College, Chulalongkorn University

Abstract

The objective of this work was to study the production of a new biodegradable mulch film. As a result of increasing problems with regards to disposal of domestic waste, particularly plastics, a new class of polymers especially designed to be biodegradable, has been undergoing development. However, biodegradable plastics still have a limitation, i.e. high cost. In this research work, how to lower the cost of biodegradable plastic and improve some properties by using epoxidized natural rubber as secondary polymer for polymer blends, was studied. Thus, the polymer blend of poly (lactic acid) (PLA) and epoxidized natural rubber (ENR) was intended for use as agricultural mulch film. The heat stabilizer and UV absorber were added to increase UV resistance of this product. The mulch film were fabricated by using a twin-screw extruder followed by a chill roll cast film extruder. The ratios of PLA and ENR investigated are 50/50, 60/40, 70/30, 80/20 and 90/10. The mechanical, thermal and morphological properties including the thickness, opacity and density of the biodegradable mulch film was evaluated and compared to traditional polyethylene film.

Keywords: Biodegradable plastics, Polymer blends, Poly (lactic acid) (PLA), Epoxidized natural rubber (ENR), Mulch film

C-2

Preparation and Characterizations of PLA Composite Loaded Hydrophobic Chitosan: Melt mixing and Solution mixing

Krisana Siralertmukul1, Phiangrawee Noknoi2,and Kawee Srikulkit2

1 Metallurgy and Materials Science Research Institute Chulalongkorn University, Bangkok 10330, Thailand (E-mail: [email protected])

2 Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok, Thailand

Abstract

Hydrophobic chitosan, HBCS was prepared as additive filler for polylactic acid, PLA, film. HBCS was prepared by a mechanical mixing of aqueous chitosan with sodium dioctyl sulfosuccinate using the chitosan to dioctyl sulfosuccinate (ratio of 1:3). The resultant HBCS was further mixed with poly(lactic acid) using solution mixing and melt mixing method. From solution mixing, PLA to HBCS ratios of 90: 10, 80: 20 and 75: 25 were employed. ATR/FTIR spectra of HBCS revealed that the hydroxyl group on the surface of hydrophobic chitosan markedly decreased, indicating an increased hydrophobicity as a result of the coverage of dioctyl sulfosuccinate. From the DSC results, PLA/HBCS exhibited two peaks of melting temperatures at 242oC and 149oC, respectively. Melt mixing of PLA and hydrophobic chitosan was then conducted using twin screw extruder in order to obtain PLA composite with improved properties (mechanical properties and antimicrobial activity). Characterization techniques including TGA, DSC and XRD were employed to investigate the structure of the polymer composite.

Keywords: Hydrophobic chitosan, Sodium dioctyl sulfosuccinate, PLA

C-3

Bio-packaging Film from Poly (lactic acid) Blends and Composites

Piyawan Pukpanta1, Wanchana Somboon1, and Kalyanee Sirisinha1, 2

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

Abstract

Environmental responsibility is constantly increasing in importance to both consumers and industry. Biodegradable poly (lactic acid) or PLA is of interest in this research. The aims of the research are two-fold. First, the methods of improving melt strength and flexibility of PLA blown films are focused on. In this part, the reactive blends of PLA and poly (butylene adipate-co-terephthalate) or Ecoflex were prepared in a twin-screw extruder in the presence of peroxide. The morphology, rheology and tensile properties of compression-moulded and blown film samples were investigated. The results showed a significant improvement in melt strength of the blends. The blends also showed comparable tensile properties to the commercial poly (ethylene) films. The second aim of this research is to improve the water vapor and oxygen barrier properties of the blend films by introducing bentonite clay into the systems. The presence of clay is believed to result in biocomposite films of increasing in modulus and thermal stability. The permeation of water vapor and oxygen gas should also be reduced. In this ongoing work, apart from the mechanical and barrier properties, the structure of the biocomposites will also be characterised using microscopy and spectroscopy techniques.

Keywords: Poly (lactic acid), Biodegradable blend, Clay, Property, Film

C-4

Green Composite Film of Polylactic Acid and Microcrystalline Cellulose

Duangdao Aht-Ong1,2, Voravadee Suchaiya1,2, Tanawat Tayommai1,2,and Dhananya Masamran1,2

1 Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok 10330 Thailand (E-mail: [email protected])

2 Research Unit of Advanced Ceramic and Polymeric Materials, National Center of Excellence for Petroleum, Petrochemicals, and Advanced Materials, Chulalongkorn University, Bangkok 10330, Thailand

Abstract

Polylactic acid (PLA), one of the most promising biodegradable plastics, has received much consideration lately as an alternative to non-biodegradable synthetic polymers due to its comparable properties and biodegradability. Although PLA has many advantages and can be used in different fields, low toughness and high cost limit its applications. Blending PLA with renewable resource as natural fiber is one of interesting approaches to reduce this problem because of its numerous advantages, such as low cost, low density, high toughness, acceptable specific strength, and biodegradability. Hence, composites of PLA and natural fiber should provide cost-performance benefits with enhanced biodegradability. Therefore, this paper presents our most recent effort to develop biodegradable plastics films from PLA and microcrystalline cellulose (MCC) at various MCC content (i.e., 0 to 40 %wt) and to investigate an aerobic biodegradation of the films under controlled composting condition according to the ISO 14855-2. Banana stem and coconut fibers including waste cotton fabric were selected as cellulose-enriched agricultural and textile wastes due to their high cellulose content. The prototype of biodegradation testing unit - Gravimetric measurement respirometric (GMR) system - was successfully set up according to the ISO 14855-2. Preliminary results revealed that 40/60 MCC/PLA biocomposite films were successfully prepared.

Keywords: Polylactic acid, Microcrystalline cellulose, Biodegradable polymers, Composite, film

C-5

Mechanical Properties of Polylactic acid/Poly(butylenes adipate-co-terephthalate)/Calcium Carbonate Composites

Arpaporn Teamsinsungvon1,2, Yupaporn Ruksakulpiwat1,2, and Kasama Jarukumjorn1,2

1 School of Polymer Engineering, Institute of Engineering, Suranaree University of Technology, Nakhon Ratchasima, Thailand (E-mail: [email protected])

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

Abstract

Polylactic acid (PLA)/poly (butylene adipate-co-terephthalate) (PBAT) blend and its composites were prepared using melt mixing process. The blend of PLA and PBAT exhibited higher elongation at break but lower tensile strength and Young’s modulus than the pure PLA. Therefore, calcium carbonate (CaCO3) was incorporated into PLA/PBAT blends at 5, 10, 20 and 30 wt% to balance properties of the blend. In addition, PLA grafted with maleic anhydride (PLA-g-MA) was added as a compatibilizer into the composites. With increasing CaCO3 loading, Young’s modulus of the composites increased while tensile strength and elongation at break decreased. It was revealed from SEM micrographs of the composites that texture of fracture surfaces had been changed with the presence of CaCO3.

Keywords: Polylactic acid, Poly (butylene adipate-co-terephthalate), Calcium carbonate, Polylactic acid grafted with maleic anhydride

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C-6

The Study of Using Glycidyl Methacrylate Grafted Natural Rubber as an Impact Modifier of Polylactic Acid

Punmanee Juntuek1,2, Chaiwat Ruksakulpiwat 3, Praneee Chumsamrong1,2

and Yupaporn Ruksakulpiwat1,2

1 School of Polymer Engineering, Institute of Engineering, Suranaree University of Technology, Nakorn Ratchasima 30000, Thailand

2 Center of Excellent for Petroleum, Petrochemical and Advanced materials, Chulalongkorn University, Bangkok 10330, Thailand

3 Department of Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand

Abstract

Natural rubber (NR) was melt blended with polylactic acid (PLA) at various ratios using an internal mixer. The impact strength and elongation at break of PLA/NR blend increased with increasing NR content up to 10% (w/w). Glycidyl methacrylate grafted natural rubber (NR-g-GMA) was melt blended with PLA/NR blends. The effect of content and %grafting of NR-g-GMA on mechanical properties of PLA were studied. The addition of NR-g-GMA in PLA/NR blend improved impact strength and elongation at break of PLA/NR blend compared to that of neat PLA and PLA/NR blend without NR-g-GMA. However, it was found that impact strength and elongation at break of PLA/NR blend increased with increasing NR-g-GMA content up to 1% (w/w) and after that it decreased. Moreover, impact strength and elongation at break of PLA/NR blend increased with increasing %grafting up to 4.35%.

Keywords: Polylactic acid, Natural rubber, Polymer blend, Reactive blending

C-7

Effect of Antioxidant Contents on Water Vapor Transmission Rate and Sorption Isotherm of Cassava Starch-Carboxymethyl

cellulose (CMC) Films

Wirongrong Tongdeesoontorn1 Lisa J. Mauer2, Sasitorn Wongruong3

and Pornchai Rachtanapun4*

1 Department of Biotechnology, Graduate School, Chiang Mai University, Chiang Mai, Thailand 2 Department of Food Science, Purdue University, IN, USA3 Division of Biotechnology, Faculty of Agro-Industry, Chiang Mai University, Chiang Mai,

Thailand,4 Division of Packaging Technology, Faculty of Agro-Industry, Chiang Mai University,

Chiang Mai, Thailand * Corresponding author: Pornchai Rachtanapun (E-mail: [email protected])

Abstract

The moisture sorption isotherm and water vapor transmission rate (WVTR) of cassava starch-carboxymethyl cellulose (CMC) films with various antioxidants (quercetin and Tertiary buthyl hydroquinone, TBHQ) contents were studied. Moisture sorption isotherm of cassava starch-CMC films were investigated at various relative humidities (0, 11, 33, 54, 75 and 95 %RH) at 25�1�C. The equilibrium moisture content of films dramatically soared above aw = 0.54. Cassava starch-CMC film with quercetin and TBHQ gave higher moisture sorption than cassava starch-CMC film without antioxidant. BET model was found to be the best-fit model for cassava starch-CMC films both with and without antioxidants. Water vapor transmission rate (WVTR) of film samples was performed at 33% and 54% relative humidity (RH) at 25�1�C. WVTR of cassava starch-CMC films increased with addition of antioxidants. WVTR of cassava starch-CMC films containing antioxidant at 54 %RH were higher than WVTR of films at 33%RH.

Keywords: Cassava starch, Carboxymethyl cellulose, Antioxidant, Water vapor transmission rate, Sorption isotherm

C-8

Electrospun Nanofibrous tissue scaffold

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

1 Cassava and Starch Technology Research Unit, National Center for Genetic Engineering and Biotechnology, Bangkok, Thailand ([email protected])*

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

3 Department of Biotechnology, Kasetsart University, Bangkok, Thailand

Abstract

Nanofibers attract many applications - such as filtration, application in life science, micro/nano electronic sensor, and military protective clothing - for making nanofibers due to its large surface area per unit mass. The most promising process among others, e.g., chemical vapor deposition, electrical arc discharge, and self assembly nanostructure, is an electrospinning process. In a fabrication point of view, electrospinning process offers low temperature process, ease of process set up modification, multiple process parameters, continuous fibers, and different fiber morphology, while other processes exhibit only some of them. Tissue scaffold is one of many life science applications that use electrospinning process for making fibrous tissue scaffold, due to connected pore in fiber sheet, controlled fiber size and characteristic, and fiber alignment. Despite the great interest in development of tissue scaffold fabrication, research and development of material for tissue scaffold shows a great emphasis for this field. Synthetic biodegradable polymer – Polylactic acid, Polycarpolactone, and Polyglycolic acid – and natural polymer – Chitosan, Starch, and Cellulose – are widely used as a material for making tissue scaffold. Starch has been introduced to this application to modify tissue scaffold wettability and degradation due to its hydrophilic and naturally degradable which are required properties of tissue scaffold.

Keywords: Electrospinning, Tissue scaffold, Starch, Fibers

C-9

Toughness Improvement by Blending Polyhydroxybutyrate-co-hydroxyvalerate with Natural Rubber (Hevea brasiliensis)

Chutamas Maneewong1, Roungrong Thongtan1, Klanarong Sriroth1

and Phiriyatorn Suwanmala2

1 Department of Biotechnology, Faculty of Agro-Industry, Kasetsart University, Bangkok 10900, Thailand (E-mail:[email protected])

2 Nuclear Research Center, Chatuchak, Bangkok 10900, Thailand

Abstract

Aimed to improve toughness of polyhydroxybutyrate-co-hydroxyvalerate(PHBV), dry natural rubber (NR) and powder PHBV were dissolved in chloroform and casted into films. The films were then irradiated by gamma-ray radiation from 60Co source at doses 10kGy, 20kGy and 30kGy. Toughness of un-irradiated samples was found to increase with increasing rubber content, implied by elongation at break improvement from 49.0�17.1% for 0% NR to 666�86% for 30% NR. However after gamma-ray irradiation, elongation at break reduced significantly for all PHBV samples that contained NR, especially at doses 20kGy and 30kGy. With an attempt to detect changes to PHBV component from being exposed to gamma-ray radiation, thermal properties of both un-irradiated and irradiated films were compared. Thermal analysis suggested that percent crystallinity of samples before and after irradiation was almost the same and there was no significant shift of melting peak, which ranged 168-171oC. However, an emerging of a small shoulder peak near 160oC for all irradiated samples suggested a shift in perfection and stability of PHBV crystals, hinted PHBV crosslinking and chain scission. In order to monitor changes to NR component, the casted films were etched by toluene and were examined via a scanning electron microscope (SEM). SEM micrographs illustrated a diminishing of NR domain, which was soluble in toluene, after the exposure to gamma-ray radiation at 20kGy indicating a change in chemical structure of NR after irradiation. The toluene-insolubility of NR domain suggested crosslinking of NR. The elongation at break of all films exposed to gamma-ray radiation at 20kGy confirmed the loss in NR elongated property since all tensile properties were comparable to the 100% PHBV film which was un-irradiated.

Keywords: Polyhydroxyalkanoates, Polyhydroxybutyrate-co-hydroxyvalerate,Natural rubber, Blend, Toughness, Crosslink, Radiation

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C-10

Properties and Processing of Glutinous Rice Starch Foam Added Natural Fiber

Napawan Kositruangchai, Pornpen Sang-on, and Patcharakamon Waewcharoen

Division of Packaging Technology, Faculty of Agro-industry, Chiang Mai University, Chiang Mai 50100 Thailand (E-mail:[email protected])

Abstract

Recently, plastic foam especially, expanded polystyrene foam (EPS) is widely used for single use due to low price, easy to use but it is one of the main pollution problems in which is difficult and also need long time to degrade. Starch based foam is one of the replacement materials EPS. The disadvantages of starch foams are brittle, poor mechanical properties and hydrophilicity therefore, in this research developed and studied the effect of fiber ratio, processing condition on foam properties using Compression Molding Machine. The results showed that the percent of fiber increased, density, flexural strength and flexural stress tended to increase. On the other hand, water absorption and flexural strain decreased and cell size got smaller.

Keywords: Starch, Starch foam, Biodegradable plastic, Fiber

C-11

Effect of Particle Size on Mechanical Properties of Biobased Composite from Oil Palm Waste

Roungrong Thongtan and Klanarong Sriroth

Department of Biotechnology, Faculty of Agro-Industry, Kasetsart University, Bangkok 10900, Thailand (E-mail: [email protected])

Abstract

In an attempt to utilize by-product biomass from agricultural industry, oil palm waste was used as filler in poly(butylene adipate-co-terephthalate) (PBAT) polymer matrix. The objectives of this study were to investigate the effect of particle size of the lignocellulosic filler and filler content on tensile properties of the biobased composite. Palm waste was milled, and sized by sieves to obtain three groups of particle size with the longest dimensions approximately 798 �m, 50.1 �m, and 47.0 �m with aspect ratios of 1.61, 1.80 and 1.80 respectively. The filler was distributed in PBAT by an extruder at 155 °C and at filler content of 0 wt%, 5 wt%, 10 wt% and 20 wt%. The palm fiber-plastic composite was pressed and cut into dumbbell-shaped tensile specimens. The tensile test results showed that, upon increasing filler content, elastic modulus of the composite increased while ultimate tensile strength and elongation at break decreased. The composite with larger particles appeared to have slightly higher elastic modulus than those with smaller particles. However, the composite containing large particles exhibited reduction in ultimate tensile strength and elongation at break by half, while those materials containing smaller particles steadily declined in both properties. Tensile-fracture surface and knife-cut surface of the composite viewed under a scanning electron microscope indicated poor wetting of the palm fiber possibly due to residual oil, moisture in fiber and irregular shapes of the fiber. Electron micrographs also revealed that filler was porous, which gave excellent stiffness-to-weight ratio.

Keywords: Palm, Lignocellulosic, Size, Tensile, Composite, Biomass, Biodegradable

C-12

Effect of Corn Husk and Rice Straw Pulp Mixing Ratio on Carboxymethylcellulose (CMC) Film Properties

Suphat Kamthai, Kraiwet Kabtum and Tanutta Hongron

Division of Packaging Technology, School of Agro-Industry,Faculty of Agro-Industry, Chiang Mai University, Chiang Mai, Thailand (E mail: [email protected])

Abstract

In the present research, the rice straw and corn husk are the one of agricultural wastes which can make available by cellulose derivative production. Therefore, the important objectives of this research were focused on the utilization of corn husk and rice straw for carboxymethylcellulose (CMC) synthesis and study the effect of mixing ratio of both agricultural wastes on CMC film properties. CMC was synthesized from corn husk and rice straw pulps at 30% sodium hydroxide (NaOH) and they were blended at different ratio (corn husk (C):rice straw (R)); 100:0, 80:20, 60:40, 50:50, 40:60, 20:80 and 0:100. The resulted revealed both agricultural wastes pulp could compatibly and the morphology of CMC blend film was smoothly when the rice straw pulp ratio was higher than corn husk pulp. The mechanical properties of CMC blend film were continued to increase as the corn husk pulp ratio. In this study, CMC film 60:40 ratio had the best CMC film properties including tensile strength, elongation at break, water vapor permeability (WVP) and water solubility which were 48.07 MPa,12.17%, 12.37×10-4g.m/m2.mmHg.day and, 96.26% respectively. However, the increment of corn husk pulp presented non-significant different (p=0.05) in WVP and water-solubility of CMC film.

Keywords: Rice straw, Corn husk, Carboxymethylcellulose

C-13

Development of Rice Straw Carboxymethylcellulose (CMC) Film Properties for Anti-anthracnose Fungi in Economic Fruits

Jurmkwan Sungsuwan Suphat Khamthai and Prem Thongchai

Division of Packaging Technology, School of Agro-Industry,Faculty of Agro-Industry, Chiang Mai University, Chiang Mai, Thailand (E mail: [email protected])

Abstract

Rice straw carboxylmethylcellulose (CMC) film was developed as anti-anthracnose fungi (Colletotrichum sp.) film and the efficiency for fungi inhibition was investigated. The natural fungicide chemical; mangosteen pericarp powder was added into rice straw CMC film at different concentrations which were varied from 0 (control film) – 25,000 ppm for inhibit banana anthracnose fungi (Colletotrichum musarum) and mango anthracnose fungi (Colletotrichum gloeosporioides). After that the CMC films were placed on Potato dextrose agar (PDA) and incubated at 25�C for 48 hrs. The results indicated that the mangosteen pericarp extracted at 25,000 ppm had the best dosage for delay the growth of banana and mango anthracnose diseases.The diameters of banana and mango anthracnose colonies at 2 days were 0.58 ± 0.10 and 0.84 ± 0.14 cm, respectively. While, the diameter of banana and mango anthracnose colonies of control film were 1.80 ± 0.17 and 1.68 ± 0.30 cm, respectively.

Keywords: Mangosteen pericarp powder, Carboxymethylcellulose, Anthracnose fungi

C-14

Preparation of Polylactide/Organoclay Nanocomposite Latexes

Siriwan Phattanarudee1,2 and Karuntarut Sermsantiwanit2

1 Department of Imaging Science and Printing Technology, Faculty of Science, Chulalongkorn University, Bangkok, Thailand (E-mail: [email protected])

2 Program of Petrochemical and Polymer Science, Faculty of Science, Chulalongkorn University, Bangkok, Thailand

Abstract

Polylactide/organoclay nanocomposite latexes were prepared by emulsification-diffusion method, which consists of emulsifying a solution of biodegradable polymer and organoclay in an aqueous phase containing stabilizers. Influences of clay concentration (0-6%wt) on particle size and morphology of the latexes, and thermal property of the resultant nanocomposite films were studied. The average particle size of the nanocomposite particles were found in a range of 20-30 micron, depending on the silicate concentration. SEM micrographs revealed that the resultant microspheres attained a smooth spherical shape with different sizes. From X-ray diffraction (XRD) analysis, it indicated that the nanocomposite films contained a pattern of �-form crystallinity, while the thermal property of such films was improved compared to that of pristine film. The highest thermal stability was obtained at 6%wt of organoclay. The obtainable nanocomposite latexes are expected to serve as a new alternative biodegradable coating with enhanced thermal property.

Keywords: Polylactide, Organoclay, Nanocomposite latex

C-15

Fabrication and Characterization of Melt Spun Poly(lactic acid) Fiber

Sirisart Ouajai*, ApikomPisitwinyoo and Suracha Traiukost

Department of Industrial Chemistry, Faculty of Applied Science, King Mongkut’s University of Technology North Bangkok, Bangkok, Thailand (E-mail: [email protected])

Abstract

This research was aimed to study morphology, mechanical and thermal properties of poly (lactic acid) (PLA) fiber. The PLA fiber was spun by a single-screw extruder at various temperatures (170-210 �C). The scanning electron micrographs of fibers showed a smooth surface. An increase in extrusion temperature and screw speed resulted in a larger fiber diameters. The collection speed of spun fiber was varied from 64.2 to 89.9 m/min. The as spun PLA fiber showed a low crystallinity measured by DSC technique. The tensile strength and modulus of fiber were 23.53 MPa and 1.56 GPa, respectively. Nevertheless, the pulling of fiber through the heat tube at 90 °C and 110 °C with a drawn ratio of 1.9 to 6.0 enhanced the tensile strength and modulus of fibers. The highest values were found at the drawn ratio equal to 6.0 and 3.7 for temperature of 110 °C and 90 °C, respectively. The enhanced properties probably originated from the better chain orientation and greater crystallinity of hot drawn fibers.

Keywords: Poly(lactic acid), Melt spinning, Draw ratio

C-16

Poly(lactic acid) Composite Film for Coatings

Nantana Jiratumnukul1, Waritha Wongsasuk1,Kunakorn Siripornnoppakun, and Umawan Sakulpanich

Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand

Abstract

Modified bentonite clay was prepared by cationic exchange process and characterized by XRD. From XRD results, modified bentonite clay showed intercalation structure. Modified Clay with intercalation structure was incorporated into PLA coating formulations with various amounts of 5%, 10%, and 15%. Physical and mechanical properties of coating films were studied as a function of the amount of modified clay in coating formulations. It was found that addition of modified clay did not increase the viscosity of the formulations. The coating films showed good water resistance. However, the gloss of coating films slightly decreased as the amount of modified clay increased.

Keywords: coating film, PLA, modified clay

C-17

Natural Coloration of Poly(lactic acid) by Natural Dyed Aluminium Silicate Powder

Prapaporn Ngenkrathok1, Rattana Rattanaampha1, Wilairat Somklieng1,Bawornkit Nekhamanurak1,2, and Pajaera Patanathabutr1,2,*

1 Department of Materials Science and Engineering, Faculty of Engineering and Industrial Technology, Silpakorn University, Nakhonpathom, 73000, Thailand(E-mail: [email protected])

2 Center of Excellence for Petroleum, Petrochemicals, and Advanced Materials, Chulalongkorn University, Phya Thai Road, Bangkok, 10330, Thailand

Abstract

This research aims to improve appearance and mechanical properties of PLA by adding natural dyed aluminium silicate powder from natural resource. Silica powder, extracted from rice husk ash, was natural dyed by Sappen wood with aluminium mordant. PLA was melt blended with natural dyed aluminium silicate powder of 100-325 mesh size in a twin-screw extruder using the content of the natural dyed powder of 1, 5, and 10 wt%., and test specimen were injection molded for mechanical test. It found that color of natural dyed PLA composites was red-brown and their color became darker with respect to higher content of the natural dyed powder. Adding the natural dyed powder into PLA increased its tensile modulus and surface hardness. However, DSC results showed that the natural dyed powder decreased crystallinity of PLA. After 3 weeks of sunlight exposure, it found that natural dyed PLA composites had moderate light fastness property.

Keywords: Natural dye, Silica, Poly(lactic acid)

C-18

Eco-friendly Binder System for Powder Injection Moulding

Nutthita Chuankrerkkul

1 Metallurgy and Materials Science Research Institute, Chulalongkorn University, Phyathai Road, Bangkok 10330, Thailand (Email: [email protected])

2 Center of Innovative Nanotechnology, Chulalongkorn University, Phyathai Road, Bangkok 10330, Thailand

Abstract

A development of an eco-friendly binder system has been carried out for powder injection moulding (PIM) of metallic, ceramic, and composite materials, e.g. tungsten carbide-cobalt hardmetals, titanium, barium hexaferrite, and stainless steel-tungsten carbide nanocomposites. The binder system contains a major fraction of polyethylene glycol (PEG) and a minor fraction of a very finely dispersed polymethyl methacrylate (PMMA). PEG can be removed using water leaching technique, creating open-pore channels which allow the remaining binder, i.e. PMMA, to be removed by pyrolysis during ramping up to sintering temperature. Powder characteristics and binder compositions had an influence on the PIM process. Rate of PEG removal depends on time and water temperature employed in the experiment. Specimens retained their shape during and after leaching of the PEG. Properties and microstructure of the components were also investigated.

Keywords: Powder injection moudling, Eco-friendly binder system

C-19

Fabrication of Stearyl-Chitosan Nanoparticle by Nanoscale Radiation Induction: An Approach for Green Bio-based

Additive for Polylactic Acid

Thitirat Rattanawongwiboon1, Phiriyatorn Suwanmala2, Kasinee Hemvichian2, and Wanvimol Pasanphan1

1 Department of Applied Radiation and Isotopes, Faculty of Science Kasetsart University, Bangkok, Thailand (Email: [email protected])

2 Thailand Institute of Nuclear Technology (TINT), Ministry of Science and Technology, Nakornnayok, Thailand

Abstract

Nanoscale radiation induction technique was used to fabricate hydrophobic-side chain chitosan nanoparticle as a novel green bio-based additive for polylactic acid (PLA). Gamma radiation induced grafting of stearyl methacrylate (SMA) onto non-irradiated chitosan (CS0) and 40 kGy pre-irradiated chitosan in colloidal form (CS40). The evidence of grafting was analyzed by yield of grafting, fourier transform infrared spectroscopy (FTIR) and atomic force microscope (AFM). The effects of g-ray doses and SMA concentration on grafting yield were studied. The grafting yield increased when the g-ray doses and SMA concentration were increased to a certain amount. Lowering the chain length by 40 kGy pre-irradiation to colloidal chitosan before radiation grafting with SMA brought the higher grafting yield. The individual spherical-like nanoscale particles (<100 nm) of CS-grafted-SMA could be achieved with the diameter approximately of 50-80 nm. The CS-grafted-SMA nanoparticle showed miscible blending with PLA.

Keywords: Chitosan, Stearyl Methacrylate, Gamma Radiation, Radiation Grafting, Polylactic Acid

C-20

Thermoplastic Starch-based Materials for Packaging: Preparation and Compounding

Nattaporn Khanoonkon, Chanakorn Yokesahachart, Laddawan Songthipya, Amporn Sane, and Rangrong Yoksan

Department of Packaging and Materials Technology, Faculty of Agro-Industry, Kasetsart University, Bangkok 10900, Thailand (E-mail: [email protected], [email protected])

Abstract

Thermoplastic starch is a “green” alternative to petroleum-based plastics. It is one of the most potential bio-based and biodegradable materials recently playing an important role in packaging industries as being produced from starch which is naturally abundant, renewable, non-toxic, cheap, biodegradable and compostable. Thermoplastic starch can be thermally converted into various profiled products using conventional plastic processing and used as stand alone raw material or as blends/compounds depending on the requirements. This presentation illustrates the development of thermoplastic starch from various kinds of Thai’s crops, e.g. cassava, rice, corn and bean, and the improvement of its properties by blending and/or compounding with other polymers (e.g., PE, PP, PBAT and PLA) and additives (e.g., calcium carbonate and fibers) for a wide range of applications including packaging. Thermoplastic starch and its blends/compounds were produced by a co-rotating twin screw extruder. The obtained thermoplastic starch showed melt flow index between 0.01 and 4 g/10 min, glass transition temperature varying from 8 to 105 �C and melting temperature ranging from 130 to 220 �C. Melt flow ability of the thermoplastic starch was improved by blending with PLA, PBAT and PE, while reduced by compounding with calcium carbonate and fibers.

Keywords: Thermoplastic starch, Compounding, Blend, Poly(lactic acid), Poly(butylene adipate-co-terephthalate), Polyethylene, Calcium carbonate, Fiber, Extrusion, Packaging

Acknowledgements: This work was financially supported by the National Research Council of Thailand, the Kasetsart University Research and Development Institute, and the Commission of Higher Education, Ministry of Education of Thailand (National Research University of Thailand).

C-21

Thermoplastic Starch-based Material for Flexible Packaging

Sarekha Woranuch, Chindawan Punchangcharoen, Ornwaree Ratcharak, Amporn Sane, and Rangrong Yoksan


Abstract

Over the last decades, the consumption of flexible packaging has continuously increased due to its light weight, good strength, and convenient transportation. Flexible packaging is mainly produced from non-biodegradable petroleum-based plastics such as PE and PP, causing environmental impacts. This can be overcome by partial/full substitution with biodegradable materials. Among the biodegradable plastics, thermoplastic starch (TPS) is a potential candidate due to being produced from starch which is naturally abundant, renewable, non-toxic, cheap, biodegradable and compostable. However, TPS is moisture sensitive and its mechanical and barrier properties vary depending on its moisture content. This presentation thus illustrates the potential and processability of TPS-based blends/compounds/composites for flexible packaging application. The effects of PLA, PBAT, PE, calcium carbonate and fibers on mechanical and barrier properties of the TPS-based materials are also reported. TPS-based materials were able to be converted into cast film/sheet and blown film using extrusion processes. TPS exhibited tensile strength, modulus and elongation at break in the ranges of 2�6 MPa, 20�45 MPa, and 90�400%,respectively. Blending with PBAT and PE improved the tensile properties of the TPS, while incorporating PLA, calcium carbonate and fibers only increased tensile strength and rigidity. Water vapor barrier property of the TPS was enhanced by blending/compounding with PLA, PBAT, PE, calcium carbonate and fibers. Oxygen barrier property of TPS was improved after incorporating with PLA and calcium carbonate, whereas deteriorated after blending with PBAT, PE and fibers. The TPS-based sheet/film can be further improved for high moisture barrier and antioxidant active flexible packaging by application of nanotechnology.

Keywords: Thermoplastic starch, Compounding, Blend, Composite, Poly(lactic acid), Poly(butylene adipate-co-terephthalate), Polyethylene, Calcium carbonate, Fiber, Extrusion, Film blowing, Flexible packaging, Sheet, Film


C-22

Thermoplastic Starch-based Materials for Rigid Packaging

Sumana Kunathan, Ranumas Thipmanee, Jitrawee Suk-em, Amporn Sane, and Rangrong Yoksan


Abstract

Thermoplastic starch (TPS) has been used as a biodegradable packaging material to substitute petroleum-based plastics and reduce the environmental impacts. However, the utilization of TPS for rigid packaging is limited due to its poor mechanical properties and high moisture absorption. Blending with other biodegradable polymers (e.g. PLA and PBAT), or additives (e.g. fibers and calcium carbonate) is an alternative to improve the properties of TPS. This presentation thus illustrates the potential and processability of biodegradable TPS-based materials for rigid packaging application. The effects of PLA, PBAT, calcium carbonate and fibers on mechanical properties of the TPS-based materials are also reported. TPS-based blends/compounds/composites were able to be converted into various profiled products including saucers, cups, trays, utensils, cans with screw caps, etc. using injection molding process. TPS exhibited tensile strength, modulus and elongation at break in the ranges of 0.25�2.12 MPa, 0.71�10.14 MPa, and 145.17�190.35%,respectively. Blending with PLA improved both tensile strength (up to 20 MPa) and rigidity (up to 1450 MPa), while decreased extensibility (~6 times) of the TPS. The incorporation of fibers also enhanced tensile strength and rigidity, but reduced extensibility of TPS. In contrast, the extensibility of TPS was significantly increased by blending with PBAT up to 500%.

Keywords: Thermoplastic starch, Compounding, Blend, Composite, Poly(lactic acid), Poly(butylene adipate-co-terephthalate), Extrusion, Injection molding, Rigid packaging, Biodegradability


C-23

Preparation of Poly(lactide)-b-Poly(butadiene)-b-Poly(lactide) for PLA impact modifiers

Na-Youn Kim, Jae-Yun Lee, Chantiga Choochottiros and In-Joo Chin*

Department of Polymer Science and Engineering, Inha University, Incheon, 402-751, KOREA

Abstract

Polylactide (PLA) is an aliphatic polyester derived from renewable resources such as corn, and it can ultimately be degraded under compositing conditions. However, PLA has drawbacks, for example, brittleness, low crystallization rate and low impact strength. In this work, PLA was copolymerized with polybutadiene (PBD) to improve the impact properties. Triblock copolymers of poly(lactide)-b-poly(butadiene)-b-poly(lactide) (LBDL) were obtained by the ring opening polymerization of lactide using tin 2-ethylhexoate (SnOct2) as catalyst and hydroxyl telechelic polybutadiene (HTPBD). HTPBD was macroinitiator, which was synthesized by ring opening metathesis polymerization. The chemical structure of LBDLwas controlled by changing lactide end blocks, while keeping the middle butadiene (BD) clock constant. The composition and thermal stability of various LBDL were characterized by TGA. The mechanical properties of these materials were examined by UTM and Izod test.

Keywords: Lactide, Butadiene, Triblock copolymer, Impact modifier

C-24

Effects of MA-g-PLA compatibilizer on PLLA/Starch Blending

Sutawan Buchatip, Monchai Tajan, Phasawat Chaiwutthinan, Kongkiat Kongsuwan, Thanawadee Leejarkpai and Atitsa Petchsuk

National Metal and Materials Technology Center (MTEC) 114 Thailand Science Park, Paholyothin Rd., Klong Luang, Pathumthani, Thailand 12120

Abstract

PLA has high mechanical properties, good biocompatibility and biodegradability despite its brittleness, low thermal stability and durability. Although the toughness and elongation can be improved by copolymerization, the cost of the production is still high. Blending is an alternative method for improving properties of PLA with low production cost. Starch, an inexpensive natural biopolymer, is a good candidate for blending with PLA. However they are immiscible blending causing the weakening of the interfacial fracture strength. To create the interface adhesion between PLA and starch, the compatibilizer is used. In this research, we grafted various percentages of maleic anhydride (0.5, 1, 2.4%) onto PLA polymer chains via free radical polymerization using peroxide and used as compatibilizer. Parameters including initiator concentration, reaction time, temperature, reaction processes (either by bulk or solution process) and monomer concentration has been investigated. Blending of various ratio the resulting graft copolymers with starch in binary system as well as ternary blend of 50/50 commercial PLA/starch with various weight ratios (0.5, 1, 2, 5 and 10%) of 2.4% MA grafted PLA was studied using internal mixer or mini extruder. Result from Scanning Electron Microscopy (SEM) indicated that the miscibility of starch/PLA blending was improved, especially in the ternary blending of starch, commercialized PLA and copolymer which acts as a compatibilizer. For binary blending of 85/15 and 70/30 starch and copolymer, it was shown that the miscibility of the polymer blend depends on MA grafting percentage as well as ratio and molecular weight of the copolymer. The miscibility of the polymer blend increased as MA grafting percentage increased from 0.5 to 2.4% while copolymer with molecular weight of 30,000 g/mol showed better miscibility than that of 15,000 g/mol. Mechanical properties such as modulus and tensile strength of the polymer blend were improved whereas the elongation at break was weakened due to the stiffness of the polymer blend. The highest modulus and tensile strength of the polymer blend was obtained in 50/50 starch/commercial PLA ternary blend as 0.5 weight ratio of copolymer compatibilizer was employed. These modulus and tensile strength of 11,145 and 203 MPa, respectively were higher than that of 50/50 commercialized PLA/starch blend (8,912 and 160 MPa, respectively).

Keywords: Maleic anhydride, Compatibilizer, Free radical polymerization, Blending

C-25

Morphology and Properties of Polylactic Acid/Thermoplastic Starch Blends

Natphichon Budtri1, and Weerasak Lertsiriyothin 2

1 School of Mechanical Engineering, Institute of Engineering, Suranaree University of Technology, Nakhon Ratchasima, Thailand. 30000

2 School of Agricultural Engineering, Institute of Engineering, Suranaree University of Technology, Nakhon Ratchasima, Thailand. 30000 (E-mail: [email protected])

Abstract

This work is to study about compatibilization of polylactic acid (PLA)/ thermoplastic starch (TPS) blends and to obtain their thermal and physical properties. TPS was prepared by twin-screw extrusion process and then to blend into the PLA with internal mixing process. The studied ratios of TPS to PLA were ranged from 30-50 % by weight. The morphological, mechanical properties and thermal properties were examined by using microscope, universal testing machine and differential scanning calorimetry (DSC) respectively. DSC data showed that all of the PLA/TPS blended ratios had decreased glass transition temperature (Tg) and melting temperature (Tm), but the effective level of TPS composition is relatively high to reduce the Tg of polymer blend. The mechanical Properties showed that tensile strength, elongation at break, Young’s modulus of the blends were at a decreasing value comparing to PLA sample. However, the morphological study revealed that PLA and TPS were not well compatibilized, especially for the high level of TPS composition sample.

Keywords: PLA, Thermoplastic starch, Mechanical Property, Thermal property

C-26

Mechanical, Thermal and Rheological Properties of Modified Poly lactic acid

Kwan-ho Seo1*, Yang-gon Goo1, Sung-Soo Kim2 and Gi-ryong Ha3

1 Department of Polymer Science, Kyungpook National University, Daegu, Korea 2 Department of Chemical Engineering, Keimyung University, Daegu, Korea 3 Advanced Material Division, Korea Research Institute of Chemical Technology,

Daejeon, Korea

Abstract

In this study, dicumyl peroxide (DCP) and ethylene glycol (EG) have been selected to induce the crosslinking of PLA for improving melt viscosity by melt processing with an internal mixer. In order to investigate the effect of two modifiers, DCP and EG, on PLA, the mechanical, thermal, and rheological properties of the modified PLA were characterized. Alcohols with different number of reaction centers reduced the PLA molecular weight by alcoholysis. The main advantage of this type of oligomer is that copolymers synthesised in the next step can be crosslinked. Also, it can be the low molecular weight plasticizer. Mixing torque increased, and melt flow index decreased with the addition of DCP as branched or crosslinked by radical coupling reaction. However, increasing the EG contents, the results were opposite. Gel content was detected for DCP and EG content. However, modified PLA without EG was detected low gel content. This proves that EG increased the more crosslinking point during the mixing of PLA. Compared to the plain PLA, such modified PLA, showed higher Tg and low crystallization rate because of the crosslinked chain. A significant decrease in the Tm was also observed for increasing DCP content as a result of the introduction of defects in the crystal lamellae by crosslinking after modification. The introduction of crosslink structure into PLA results in the increase of the tensile modulus and the decrease of elongation at break. This may be attributed to the crosslinking structure which stiffens the PLA. However, the increase of gel content and crosslink density made the crosslinked PLA more brittle. An increase in storage modulus (G'(�)) and complex viscosity (�*) at low frequencies showed that the modified PLA turned from a liquidlike to a solidlike state by modification with DCP and EG. The higher viscosity allowed the production of PLA foams with smaller cell size and lower blowing ratio compare to plain PLA.

Keywords: PLA, DCP, Ethylene glycol, Croosslinking

C-27

Enhancement of Miscibility between Poly (Lactic Acid) and Starch Surface Modified with Silane Coupling Agents

Piyawanee Jariyasakoolroj1, Suwabun Chirachanchai1, 2,*

1 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, Thailand 2 Center for Petroleum, Petrochemical, and Advanced Materials, Chulalongkorn University,

Bangkok, Thailand (E-mail: [email protected])

Abstract

Starch is a potential bio-filler for incorporation with poly(lactic acid) (PLA) due to its naturally availability and biodegradability. Unfortunately, the strong hydrogen bonds among starch chains obstruct the melt and initiate miscible blend with any compounds.1 In the past, a number of compatibilizers such as maleic anhydride, acrylic acid, etc., were developed so as to overcome the phase separation. However, the use of chemicals may involve with toxicity and multi-steps treatment which is not practical in industrial scale production.2-3 As organosilane coupling agent is known for its effectiveness in coupling of two species, either organic or inorganic compounds, we, thus, focus on the use of this coupling agent to modify the starch surface with hydrophobic group for the compatibility with PLA. Figure 1 shows degree substitution of three types of silanes onto starch under the various concentrations of silane in the system as clarified by 1H NMR. The morphology observation using SEM confirms that starch coupled with silane C gives good miscibility in the blend with PLA (Figure 2) as compared to other systems. The presentation covers the effect of silane on starch based on the crystallization behavior.

Figure 1. Degree substitution of silane in starch Figure 2. SEM micrographs of the blend systems molecules ( silane A, silane B, and of PLA with: (a) starch, and starch surface

silane C). modified with (b) silane A, (c) silane B, and (d) silane C.

Keywords: Poly(lactic acid), modified starch, compatibilization, miscibility, silane coupling agent

References 1. A.R. Rahmat, W.A. Rahman, L.T. Sin, A.A. Yussuf, Mater. Sci. Eng. C, 29 (2009) 2370. 2. J.F. Zhang, X. Sun, Biomacromolecules, 5 (2004) 1446. 3.�S.W.�Chin,�J.�Macromol.�Biosci.�5�(2005)�352.�

C-28

Conjugating Starch on Poly(butylene succinate): A Simple Approach to Prepare PBS Masterbatch

Kanitporn Suchao-in1, Piyawit Koombhongse2, Suwabun Chirachanchai1, 3*

1 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand2 National Metal and Materials Technology (MTEC) 3 Center for Petroleum, Petrochemical, and Advanced Material, Chulalongkorn University,

Bangkok 10330, Thailand [email protected]

Abstract

Poly(butylene succinate), PBS, is one of the promising synthetic biodegradable aliphatic polyesters which applications of films and sheets were proposed. It shows high flexibility, excellent impact strength, and thermal and chemical resistance. This results in the advantages of mechanical strength when blending with other biodegradable resins, especially PLA products. PBS itself has some limitations in blow-molded or extruded product because of its low melt strength and viscosity and also high cost. The strategies to develop value added product by bringing in the additives to reduce the cost and functionalizing PBS to increase the melt viscosity are important. Starch is a considerable additive not only reduces the cost and increases melt viscosity but also increase crystallization rate. To avoid immiscibility of starch and PBS in which causes low mechanical properties, compatibilizers are needed. For instance, lysine diisocyanate and glycerol were used to improve the chemical and physical compatibility, respectively. The present work proposes a simple strategy to conjugate starch on PBS by using conjugating agents in water. The research aims to clarify the optimal condition for the reactions, the consequent morphological changes (Figure 1), the thermal properties of the product obtained including the studies of the blends.

Figure 1. Spherulite formation of (a) commercial PBS and (b) PBS-starch at 80oc, 120 sec.

Keywords: Poly(butylene succinate), Starch, Conjugating reaction

(a) (b)

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54

Session: D

Degradation and Standards

D-1

Biodegradability Test of PLA-based Composites by ISO 14855-2

Napakarn Kawee, Wirat Vanichsriratana, Prakit Sukyai*

Department of Biotechnology, Faculty of Agro-Industry, Kasetsart University, Bangkok, Thailand, 10900 (*corresponding author; [email protected])

Abstract

The plastic requirements of earth inhabitant are enormous and has environmental impacts of such consumption. An average person consumes many tons of those materials which ultimately disposed as wastes. Therefore, the trend of environmental awareness increases the demanding of biodegradable plastic. Presently, the outstanding biodegradable polymer is poly (lactic acid) (PLA) which derives from renewable resources by fermentation using carbohydrate materials such as corn and tapioca starches. In addition, good mechanical properties, biocompatibility and easily degrades by microorganisms in control conditions are also interested point of view. The degradation of PLA has been extensively studied in various methods. The biodegradation of PLA-based composites in aerobic condition under controlled composting system is the main focus of this research. Furthermore, we supposed that its end-of-life treatment can be completed the life cycle assessment (LCA) of those kind of products. Compost is designed to control the humidity, aeration ratio, and temperature during the test following ISO 14855-2. Microbial diversity from mature compost plays an important role to accelerate degradation. It is, therefore, an important to monitor the variety of microorganisms by genetic method during operation. Thus, our aspirations would like to provide an important data of environment effect of biodegradable products which further benefits consumers and industrial section.

Keywords: Biodegradability, Biodegradable, Poly(lactic acid), Life cycle assessment

D-2

A Comparison of Life Cycle Environmental Impact of Polylactic Acid and Polystyrene Trays

Unchalee Suwanmanee1, Maytinee Sanmaneechai1, Yosita Rudeekit2,Thanawadee Leejarkpai2, and Thumrongrut Mungcharoen1*

1 Department of Chemical Engineering, Faculty of Engineering, Kasetsart University, Bangkok, Thailand

2 National Metal and Materials Technology Center, Pathumthani, Thailand

Abstract

The objective of this study is to assess the environmental impact of the two types of tray packages using the Life Cycle Assessment technique. The materials of tray package are Polystyrene (PS) derived from petroleum and Polylactic acid (PLA) derived from corn. The functional unit is specified as 420 liters of 20 x 14 x 1.5 cm. of PLA and PS trays which weigh 15.10 and 4.03 kilograms, respectively. Assessment was done by using the SimaPro 7.02 program together with the CML 2 Baseline 2000 version 2.03 method. The study was divided into 2 parts. The first part covered the raw material production, transportation, tray production and transportation to consumers while the second part covered the waste management of tray package after the end of life. For the first part, it is found that the total environmental impact of PLA tray is 2.57 times more than the PS tray. The main impacts are marine aquatic ecotoxicity, human toxicity and global warming. In the second part of the study, various waste management scenarios were considered. The results show that composting is the best waste management method for PLA tray and can reduce the environmental impact by 13.4%. For PS tray, incineration with heat recovery is the best and can reduce the environmental impact by 6.8%. Considering the whole life cycle, typical PLA tray with composting has higher environmental impact than the PS tray with incineration and heat recovery. However, PLA tray with process improvement, by using biomass feedstock for PLA production and reducing the amount of raw material used in the forming process, has lower life cycle environmental impact than the PS tray.

Keywords: Life Cycle Assessment, Polylactic acid, Polystyrene, Tray, Waste management

D-3

Application of Life Cycle Assessment Technique to Polylactic Acid (PLA) and its Products Produced in Thailand

Pomthong Malakul1,2, Seksan Papong1, Tassaneewan Chom-in1, Warunee Likitsupin1,Pechda Wenunun1, Manit Nithithanakul2, and Ed Sarobo 3

1 Environmental Management Lab, National Metal and Materials Technology Center (MTEC), Pathumthani, Thailand (E-mail: [email protected])

2 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, Thailand 3 Department of Plant Farm, Faculty of Agriculture, Kasetsart University, Bangkok, Thailand

Abstract

Over 2.7 million tonnes of plastic waste is generated each year in Thailand. From this amount, only 0.2 million tons or approximately 10% is recycled. The rest is sent to landfills where it may take several hundred years for plastic wastes to be degraded biologically. This presents serious environmental problems that need to be taken care of urgently. In addition, as conventional plastics are produced from petroleum through petrochemical processes, they can generate greenhouse gases (GHGs) to the environment. As a result, bio-based plastics are increasingly considered as an environmental friendly alternative to petroleum-based plastics. Since Thailand has abundant natural biomass resources, there are great potentials to convert these resources to eco-friendly products such as bioplastics which are biodegradable in nature and with a potential to reduce GHGs. In this aspect, polylactic acid (PLA) production from cassava is one of the most promising bio-based materials for petroleum-based plastic substituting in Thailand. The goal of this study is to evaluate the environmental performance of PLA from cassava by using life cycle assessment (LCA) technique. The system boundary is designed to cover all phases throughout the life cycle of PLA, including cassava cultivation, starch production, lactic acid and PLA production, PLA processing, use, and disposal. The functional units are defined as one kg of PLA and individual selected PLA products. The results are presented for relevant environmental impact categories such as greenhouse gases, acidification, eutrophication, energy resources, etc. The environmental performance of the bioplastic will be compared with that of conventional plastics and used to provide suggestions for the improvement of bioplastic to be more environmental friendly.

Keywords: LCA, PLA, Cassava, Greenhouse Gases

D-4

Biodegradation of PLA and PLA/Starch Blends in Landfill and Controlled Composting Conditions

Yosita Rudeekit, Pongsak Siriyota, Monchai Tajan, Phasawat Chaiwuttinan and Thanawadee Leejarkpai

National Metal and Materials Technology Center, 114 Thailand Science Park Phahonyothin Rd., Klong 1, Klong Luang, Pathumthani 12120 Thailand

Abstract

In Thailand, most plastic waste ends up in landfills as a general process of municipal waste collection. This paper investigated the biodegradation performance of polylactic acid (PLA) and PLA/Starch blend with various amounts of starch content under real landfill conditions, and the results were compared with the results from a test method for evaluating biodegradation under controlled composting conditions according to ASTM D5338. The results obtained from the landfill conditions showed that PLA/starch blends were degraded relatively more rapid than PLA itself. The initial degradation of PLA and PLA/starch blends was observed approximately 3 months after buried in the landfill. Moreover, the results showed that the degradation and disintegration of the blend samples were increased as the starch contents increased. The blends were completely biodegraded and no residuals could be observed though visual inspection after 10 months. Whereas, full breakdown of PLA took place and its residual remained in the form of a white powder within 14 months. After that, no PLA residual could be visual inspection within 16 months of testing. Moreover, the percentage of biodegradability was obtained by determining the percentage of carbon in the test sample that was converted to CO2 during the duration of the test. The degree of biodegradation for 120 days of PLA and PLA/starch blend (50:50) were 85.75% and 93.60%, respectively. The biodegradation observed for the test samples explored in this study matches well with theoretical degradation and biodegradation mechanisms. The morphology, thermal property and starch contents in the residue were studied using SEM, DSC and TGA, respectively.

Keywords: Polylactic acid (PLA), Starch, Landfill, Composting, ASTM D 5338

D-5

Determination of the Aerobic Biodegradability of Polylactic Acid and Starch Co-Extruded Material in an Aqueous Medium

Pongsak Siriyota, Yosita Rudeekit, Monchai Tajan, Phasawat Chaiwutthinan and Thanawadee Leejarkpai

National Metal and Materials Technology Center, 114 Thailind Science Park Phahonyothin Rd., Klong 1, Klong luang, Pathumthani 12120, Thailand

Abstract

It is known that conventional plastics are non-degradable and take along time to break down when they are environments. Single use, disposable short-life packaging material, service ware items become waste only a short time after used.Therefore, the disposal into environments of plastic waste contributes significantly to their environment impact. Biodegradable plastics would ease disputes on environment pollution and reduce reliance on fossil resources. However, biodegradable plastics are significantly more expensive than conventional plastics it has failed to win widespread consumer acceptance. Clearly starch based polymers offer a very attractive low cost for biodegradable plastics. The aim of this study was to investigate the aerobic biodegradation of PLA, PLA/starch blend with various amounts of starch content after degradation testing in an aqueous medium according to ISO 14852 at 25oC (ISO 14852: 1999 - Determination of the ultimate aerobic biodegradability of plastic materials in an aqueous medium - Method by analysis of evolved carbon dioxide). The starch used in this study was unmodified cassava starch. The blends were melt compounded using a laboratory twin screw extruder with co-rotating mixing screw. The concentrations of the starch in the blend were 30% and 50% by weight. The test samples were exposed in synthetic medium under laboratory conditions to an inoculum from compost. The percentage biodegradations after 135 days of cellulose powder as reference material, PLA, PLA/starch blend 70:30 wt% and 50:50 wt% were found to be 58.76%, 1.06%, 11.40% and 28.17%, respectively. Additionally, the number of microbial was studied. The highest number of microbial was observed in the first 10 days of the test. It had some relationships with the maximum amount of carbon dioxide evolved from these polymers.

Keywords: Polylactic acid, Starch, Biodegradation, Aqueous medium, ISO 14852

D-6

Control of Biodegradability of Poly(butylene succinate) by Addition of Cellulose Acetate Butyrate

Yuya Tachibana*, Fumi Ninomiya, Masahiro Funabashi, Masao Kunioka

National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan (*corresponding author; [email protected])

Abstract

We have evaluated the effect of addition of cellulose acetate butyrate (CAB) to poly(butylenes succinate) (PBS). PBS and CAB were mixed with a melt kneading machine or cast process. The strain and strength at break in the case of the blend with 10 % CAB in the PBS matrix were 547 % and 35 MPa. It showed that CAB acts as a plasticizer for PBS. The biomass carbon ratio of the blends measured by accelerator mass spectrometry based on ASTM D6866 showed that the biomass carbon derived from a part of the CAB corresponded to the theoretical value of the polymer blend. The biodegradation of PBS with the CAB melt blend powders was evaluated by a microbial oxidative degradation analyzer under controlled compost conditions based on ISO 14855-2. The biodegradation rate of PBS with 1 % CAB was slower than PBS without CAB. Furthermore, PBS with 5 and 10 % CAB was not degraded within 50 days. These results shows that the addition of CAB can control the biodegradability of the PBS.

Keywords: Biodegradability, Poly(butylene succinate), Cellulose acetate butyrate

-10

0

10

20

30

40

50

60

70

0 10 20 30 40 50

Deg

ree

of b

iode

grad

atio

n /%

Incubation time /day Figure 1. Biodegradation test of PBS/CAB blend at 58 oC under controlled

compost conditions based on ISO 14855-2 �; PBS,�; PBS/CAB = 90/10

blend, �; PBS/CAB = 95/5 blend, X; PBS/CAB = 99/1 blend

D-7

Biomass Carbon Ratio of Polymer Products Measured by Accelerator Mass Spectrometry

Masahiro Funabashi1*, Masao Kunioka1, Fumi Ninomiya1, Keiichi Ohara2

1 National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan (*corresponding author; [email protected])

2 Institute of Accelerator Analysis Ltd. (IAA), Shirakawa Analysis Center 6-270 Ichididan, Shirakawa, Shirakawa 961-0835, Japan

Abstract

Biomass carbon ratio of chemicals, which can be used as source materials for polymers and their composites, were measured by the accelerator mass spectrometry (AMS) method based on ASTM D 6866-08. Biomass includes 14C with constant ratio of 1 x 10-12 and petroleum includes no 14C. Biomass carbon ratio was estimated by carbon isotopes of 12C, 13C and 14C in samples by AMS measurement. Sample preparation methods of solid, liquid and gas samples related to bioplastics for AMS measurement were described. Sample preparation method of samples including carbonate such as calcium carbonate was also described. Reproducibility and repeatability of biomass carbon ratio measurement by AMS were investigated. Correction of biomass carbon ratio for samples, such as the plant materials, was investigated. Polymer blend of poly(lactic acid) (PLA) and poly(butylene succinate) (PBS) were made by casting from solution of PLA and PBS with chloroform. Repeatability of biomass carbon ratios of this polymer blend by AMS is shown in Table (a). Measured data is smaller than estimated values. It is thought that PLA is added some additives including non-biobased carbon. Composite film of PBS with cellulose powders were made by a hot-press from mixtures of PBS powders and cellulose powders. Repeatability of biomass carbon ratios of this composite is shown in Table (b). Measured data is greater than estimated values. Biomass carbon ratio of cellulose from wood is overestimated than 100 %, since higher concentration of 14C was observed in air from 1950's by atomic bomb test in atmosphere. From these results, the correction of biomass carbon ratio caused by the origin of materials is necessary.

Keywords: Biomass Carbon Ratio, Accelerator Mass Spectrometry, Polymer blend

Opening Address

Overview of AIST

Dr. Seichi AibaNational Institute of Advanced Industrial Science

and Technology


Research Topics in AIST

Seiichi Aiba

National Institute of Advanced Industrial Science and Technology (AIST)

Abstract

Overview of AIST0AIST is the largest research organization in the area of industrial science and technology

in Japan, with multidisciplinary competence in six fields: life science and biotechnology;information technology and electronics; nanotechnology, materials, and manufacturing;environment and energy; geological survey and applied geoscience; and metrology andmeasurement science.0The headquarters are located in Tokyo and Tsukuba with nine regionalcenters throughout the country from Hokkaido to Kyushu. The number of staff at AIST amountsto about 10,000, including people from the private sector and universities in Japan and overseas.Of these, about 2,300 are full-time researchers while about 700 are clerical staff. AIST isworking to serve as an advanced model for public research institutes and to function as apowerful interface for innovations by bridging academia, industry, and government so as toestablish a synergy (“open innovation hub”) through their linkage.

Toward green innovation• Development of technologies to expand the use of renewable energy• Development of energy-saving technologies• Securing of resources and development of technologies to effectively use resources• Development of technologies to reduce industrial environmental loads• Development of technologies to evaluate and manage green innovation• Development of technologies to efficiently manufacture high-quality substances using

bioprocesses that help to reduce industrial environmental loads

Research topics in bioplastics and Biobased materials• Synthesis of polyesters using maicrowave• Production of D-lactic acid and 3-hydroxy butyric acid by bioprocesses• Production of poly(3-hydroxy butyrate) by bioprocess using glycerol• Development of composites using cellulose nanofibers• Development of copolyesters using 2,5-furandicarboxylic acid• Development of biobased polyamide 4• Development of biobased thermosetting resin and anti-flamable agent• Measurement of biomass carbon ratio in biomass plastics

Powerpoint Presentation

New Pretreatment System of Biomass andHyperthermophilic Cellulases

Dr. Kazuhiko IshikawaNational Institute of Advanced Industrial Science

and Technology















Prospect of Biochemical Conversion of AgriculturalWastes to Sugars and Value-add Products

Dr. Kazuhiko IshikawaNational Institute of Advanced Industrial Science

and Technology

















Microbial Production of Glyceric and fromRaw Glycerol and its Application to Bioplastics

Dr. Tokuma FukuokaNational Institute of Advanced Industrial Science

and Technology













Fully Biomass-based Poly (Butylenes Succinate)Synthesized from Furfural and its Certification

by Accelerated Mass Spectrometry

Dr. Masao KuniokaNational Institute of Advanced Industrial Science

and Technology















Production of Propylene from Bio-ethanol

Dr. Tadahiro FujitaniNational Institute of Advanced Industrial Science

and Technology











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Processing of Bio-based Polyesters intoHigh-performance fibers

Prof. Hideki YamaneKyoto Institute of Technology





















Optimization of Lactic Acid Fermentation from LocalRaw Materials Using a Highly Effective Bacterial Strain

Dr. Sureelak RodtongSuranaree University of Technology













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Lactide Synthesis and PolymerizationUsing Novel Catalyst

Assoc. Prof. Dr. Winita PunyodomChiang Mai University















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Bio-Succinate: Metabolic Engineering Approachfor its Sustainable Production in Thailand

Dr. Kaemwich JantamaSuranaree University of Technology
















Documents

pla+phb blend composite