Food Composition and Analysis

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Many foods depend on additives for safety, stability, or preservation. Foods are packaged to protect them and keep them in good condition while they are delivered to shops, stacked on shelves, or stored at home. This volume introduces and surveys the broad and complex interrelationships among food ingredients and processing, and explores how these factors influence food quality and safety. This will be a valuable reference for professionals in food processing as well as for those working in fields that service, regulate, or otherwise interface with the food industry.

About the Editors

A. K. Haghi, PhD, holds a BSc in urban and environmental engineering from University of North Carolina (USA); a MSc in mechanical engineering from North Carolina A&T State University (USA); a DEA in applied mechanics, acoustics and materials from Université de Technologie de Compiègne (France); and a PhD in engineering sciences from Université de Franche-Comté (France). He is the author and editor of 65 books as well as 1000 published papers in various journals and conference proceedings. Dr. Haghi has received several grants, consulted for a number of major corporations, and is a frequent speaker to national and international audiences. Since 1983, he served as a professor at several universities. He is currently Editor-in-Chief of the International Journal of Chemoinformatics and Chemical Engineering and Polymers Research Journal and on the editorial boards of many international journals. He is a member of the Canadian Research and Development Center of Sciences and Cultures (CRDCSC), Montreal, Quebec, Canada.

Elizabeth Carvajal-Millan, PhD, has been working as a Research Scientist at the Research Center for Food and Development (CIAD) in Hermosillo, Mexico, since 2005. She obtained her PhD in France at École Nationale Supérieure Agronomique de Montpellier (ENSAM), her MSc degree at CIAD, and undergraduate degree at the University of Sonora, Mexico. Her research interests are focused on biopolymers, particularly in the extraction and characterization of polysaccharides of high value added co-products, recovered from the food industry, especially ferulated arabinoxylans. She has published more than 40 refereed papers, 15 chapters in books, over 60 conference presentations, and one patent.

Methods and Strategies

FOOD COMPOSITION and ANALYSIS

Methods and Strategies

Haghi

Millan

ISBN: 978-1-926895-85-7 9 781926 895857 0 0 0 0 9

Methods and Strategies

FOOD COMPOSITION and ANALYSIS

Methods and Strategies

Haghi

Millan

ISBN: 978-1-926895-85-7 9 781926 895857 0 0 0 0 9 www.appleacademicpress.com

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Food Composition and Analysis

Methods and Strategies

ISBN: 978-1-926895-85-7 9 781926 895857 0 0 0 0 9 www.appleacademicpress.com

Apple Academic Press

Methods and Strategies

and

ANALYSIS

FOOD COMPOSITION

Editors

PhD

A. K. Haghi,

Elizabeth Carvajal-Millan,

Methods and Strategies

and

ANALYSIS

FOOD COMPOSITION

Editors

PhD

A. K. Haghi,

Elizabeth Carvajal-Millan,

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FOOD COMPOSITION

AND ANALYSIS

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FOOD COMPOSITION

AND ANALYSIS

Methods and Strategies

Edited by

A. K. Haghi, PhD, and Elizabeth Carvajal-Millan, PhD

Apple Academic Press

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A. K. Haghi, PhD

A. K. Haghi, PhD, holds a BSc in urban and environmental engineering from the Uni-versity of North Carolina (USA); a MSc in mechanical engineering from North Caro-lina A&T State University (USA); a DEA in applied mechanics, acoustics and materi-als from Université de Technologie de Compiègne (France); and a PhD in engineering sciences from Université de Franche-Comté (France). He is the author and editor of 65 books as well as 1000 published papers in various journals and conference proceed-ings. Dr. Haghi has received several grants, consulted for a number of major corpora-tions, and is a frequent speaker to national and international audiences. Since 1983, he served as a professor at several universities. He is currently Editor-in-Chief of the

International Journal of Chemoinformatics and Chemical Engineering and Polymers Research Journal and on the editorial boards of many international journals. He is a

member of the Canadian Research and Development Center of Sciences and Cultures (CRDCSC), Montreal, Quebec, Canada.

Elizabeth Carvajal-Millan, PhD

Elizabeth Carvajal-Millan, PhD, has been working as a Research Scientist at the Re-search Center for Food and Development (CIAD) in Hermosillo, Mexico, since 2005. She obtained her PhD in France at Ecole Nationale Supérieure Agronomique de Mont-pellier (ENSAM), her MSc degree at CIAD, and undergraduate degree at the Univer-sity of Sonora, Sonora, Mexico. Her research interests are focused on biopolymers, particularly in the extraction and characterization of polysaccharides of high value added co-products, recovered from the food industry, especially ferulated arabinox-ylans. She has published more than 40 refereed papers, 15 chapters in books, over 60 conference presentations, and one patent.

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List of Contributors ...ix List of Abbreviations ... xv Preface ... xvii

1. Vegetable Oils as Platform Chemicals for Synthesis of Thermoplastic Bio-based Polyurethanes ...1

C. Bueno-Ferrer, N. Burgos, and A. Jiménez

2. Antioxidant Activity of Maize Bran Arabinoxylan Microspheres ...19

A. L. Martínez-López, E. Carvajal-Millan, Y. L. López-Franco, J. Lizardi-Mendoza, and A. Rascón-Chu

3. Comparative Estimation of Kalanchoe Juice Antioxidant Properties ...29

N. N. Sazhina

4. Enzymes for Flavor, Dairy, and Baking Industries ...37

Adriane B. P. Medeiros, Suzan C. Rossi, Mário C. J. Bier, Luciana P. S. Vandenberghe, and Carlos R. Soccol

5. Membrane Technology in Food Processing ...49

Cesar de Morais Coutinho

6. Tenderization of Meat and Meat Products: A Detailed Review ...95

B. G. Mane, S. K. Mendiratta, and Himani Dhanze

7. Biological Properties of Mushrooms ... 113

Carlos Ricardo Soccol, Leifa Fan, and Sascha Habu

8. Molecular and Immunological Approaches for the Detection of

Important Pathogens in Foods of Animal Origin...149

Porteen Kannan and Nithya Quintoil

9. Cross-Linking of Ferulated Arabinoxylans Extracted From Mexican Wheat Flour: Rheology and Microstructure of the Gel ...169

A. Morales-Ortega1, E. Carvajal-Millan, P. Torres-Chavez, A. Rascón-Chu, J. Lizardi-Mendoza, and Y. López-Franco

10. Free and Ester-linked Ferulic Acid Content in a Hard-to-Cook

Pinto Bean (phaseolus vulgaris l.) Variety ...181

Agustín Rascon-Chu, Karla Escarcega-Loya1, Elizabeth Carvajal-Millan, and Alfonso Sánchez

11. Polyacrylamide-Grafted Gelatin: Swellable Hydrogel Delivery System for Agricultural Applications ...187

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12. The Dynamics of Bacteria and Pathogenic Fungi in Soil Microbiocenosis under the Influence of Biopreparations Use during Potato Cultivation. ..213

V. V. Borodai

13. Irradiation of Fruits, Vegetables, and Spices for Better Preservation and Quality ...227

Md. Wasim Siddiqui, Vasudha Bansal, and A. B. Sharangi

14. Antioxidant Properties of Various Alcohol Drinks ...251

N. N. Sazhina, A. E. Ordyan, and V. M. Misin

15. A Study on the Potential of Oilseeds as a Sustainable Source of Oil and Protein for Aquaculture Feed ...269

Crystal L. Snyder, Paul P. Kolodziejczyk, Xiao Qiu, Saleh Shah, E. Chris Kazala, and Randall J. Weselake

16. Electrochemical Methods for Estimation of Antioxidant Activity

of Various Biological Objects ...283

N. N. Sazhina, E. I. Korotkova, and V. M. Misin

17. Ozonolysis of Chemical and Biochemical Compounds...299

S. Rakovsky, M. Anachkov, and G. E. Zaikov

18. Antioxidant Activity of Mint ...337

N. N. Sazhina1, V. M. Misin, and E. I. Korotkova

19. Wild Orchids of Colchis Forests and Save Them as Objects of

Ecoeducation, and Producers of Medicinal Substances ...347

E. A. Averjanova, L. G. Kharuta, А. Е. Rybalko, and К. P. Skipina

20. Fixation of Proteins on MNPs ...359

A.V. Bychkova, M. A. Rosenfeld, V. B. Leonova, O. N. Sorokina, and A. L. Kovarski

21. Antimicrobial Packaging for Food Applications ...377

S. Remya, C. O. Mohan, C. N. Ravishankar, R. Badonia, and T. K. Srinivasa Gopal

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M. Anachkov

Institute of Catalysis, Bulgarian Academy of Sciences, Sofia 1113, Bulgaria.

E. A. Averjanova

Sochi Branch of the Russian Geographical Society, 354024, Sochi, Kurortny pr., 113. E-mail: [email protected]

Tel. +7 (8622) 619857

R. Badonia

Veraval Research Centre, Central Institute of Fisheries Technology, 362 029, Gujarat.

Vasudha Bansal

Agrionics Division (DU-1), Central Scientific Instruments Organisation (CSIO), CSIR Chandigarh, India.

Mário C. J. Bier

Bioprocess Engineering and Biotechnology Department, Federal University of Paraná (UFPR), CEP 81531-990, Curitiba–PR, Brazil.

V.V. Borodai

Eco biotechnology and biodiversity department, Biotechnology faculty, National University of Life and Environmental Sciences of Ukraine, Kyiv 15, Geroiv Oborony str., Kyiv, Ukraine.

E-mail: [email protected]

C. Bueno-Ferrer

Analytical Chemistry, Nutrition & Food Sciences Department, University of Alicante, P.O. Box 99, E-03080, Alicante, Spain.

Telephone: +34-965909660 E-mail: [email protected]

N. Burgos

A. V. Bychkova

Federal state budgetary institution of science Emanuel Institute of Biochemical Physics of Russian Acad-emy of Sciences, Kosygina str., 4, Moscow, 119334, Russia.

Elizabeth Carvajal-Millán

Laboratory of Biopolymers, CTAOA. Research Center for Food and Development, CIAD, AC., Hermosillo, Sonora 83000, Mexico.

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Cesar de Morais Coutinho

Department of Food Research - Campus of Frederico Westphalen – CAFW, Federal University of Santa Maria – RS.

Himani Dhanze

Research Scholar, Department of Veterinary Public Health, College of Veterinary & Animal Sciences, CSK-HPKV, Palampur-176062, Himachal Pradesh, India.

Karla Escarcega-Loya

Laboratory of Biotechnology, CTAOV, Research Center for Food and Development, CIAD, A.C., Her-mosillo, Sonora 83000, Mexico.

Leifa Fan

Institute of Horticulture, Zhejiang Academy of Agricultural Sciences, 139 Shiqiao Road, Hangzhou-ZJ, P.R. China, 310021.

Sascha Habu

Federal University of Paraná, Dept. Bioprocess and Biotechnology. Rua Francisco H. dos Santos - Centro Politécnico, Jardim das Américas - Curitiba/Pr – Brazil.

E. A. Hassan

Department of Chemistry, Faculty of Science, AL-Azhar University, Cairo, Egypt.

A. Jiménez

Porteen Kannan

Assistant Professor Department of Veterinary Public Health and Epidemiology, Madras Veterinary College, Chennai, India.

E. Chris Kazala

Department of Agricultural, Food & Nutritional Science, University of Alberta, 4-10 Agriculture/Forestry Centre, Edmonton, Alberta, Canada, T6G 2P5.

L. G. Kharuta

Sochi Institute of Russian people’s friendship university, 354340, Sochi, Kuibyshev str., 32. Fax +7 (8622) 411043

Paul P. Kolodziejczyk

Biolink Consultancy Inc., P.O. Box 430, New Denver, B.C., Canada, V0G 1S0.

E. I. Korotkova

Tomsk Polytechnic University, 30 Lenin Street, 634050, Tomsk, Russia Е-mail: [email protected]

A. L. Kovarski

V. B. Leonova

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Y. López-Franco

Laboratory of Biopolymers, CTAOA, Research Center for Food and Development, CIAD, AC., Hermosillo, Sonora 83000, Mexico.

J. Lizardi-Mendoza

Laboratory of Biopolymers, CTAOA, Research Center for Food and Development, CIAD, AC., Hermosillo, Sonora 83000, Mexico.

B.G. Mane

Assistant Professor, Department of Livestock Products Technology.

A. L. Martínez-López

Laboratory of Biopolymers, CTAOA. Research Center for Food and Development, CIAD, AC., Hermosillo, Sonora 83000, Mexico.

Adriane B. P. Medeiros

S. K. Mendiratta

Principal Scientist, Division of Livestock Products Technology, Indian Veterinary Research Institute, Izat-nagar-243122, Uttar Pradesh, India.

V. M. Misin

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4 Kosygin Street, 119334 Mos-cow, Russia

E-mail: [email protected] E-mail: [email protected]

C.O. Mohan

Veraval Research Centre, Central Institute of Fisheries Technology, Gujarat 362 029. E-mail: [email protected]

M. S. Mohy Eldin

Polymer Materials Research Department, Advanced Technology and New Materials Research Institute, City for Scientific Research and Technological Applications, New Boarg Elarab City, 21934, Alexandria, Egypt.

A Morales-Ortega

Research Center for Food and Development, CIAD, AC., Hermosillo, Sonora 83000, Mexico,

A. M. Omer

Polymer Materials Research Department, Advanced Technology and New Materials Research Institute,City for Scientific Research and Technological Applications, New Boarg Elarab City, 21934, Alexandria, Egypt.

A. E. Ordyan

Emanuel Institute of Biochemical Physics Russian Academy of Sciences, 4 Kosygin Street, 119334 Mos-cow, Russia.

Xiao Qiu

Department of Food and Bioproduct Sciences, University of Saskatchewan, 51 Campus Drive, Saskatoon, Saskatchewan, Canada, S7N 5A8.

Nithya Quintoil

Teaching assistant Department of Veterinary Public Health and Epidemiology, Rajiv Gandhi Institute of Veterinary Education and Research, Puducherry, India.

S. Rakovsky

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Agustín Rascon-Chu

Laboratory of Biotechnology, CTAOV. Research Center for Food and Development, CIAD, AC., Hermosil-lo, Sonora 83000, Mexico.

C. N. Ravishankar

Fish Processing Division, Central Institute of Fisheries Technology, Cochin, 628 029.

S. Remya

Veraval Research Centre, Central Institute of Fisheries Technology, Gujarat 362 029.

M. A. Rosenfeld

Federal state budgetary institution of science Emanuel Institute of Biochemical Physics of Russian Acad-emy of Sciences, Kosygina str., 4, Moscow 119334, Russia.

Suzan C. Rossi

А. Е. Rybalko

Sochi Institute of Russian people’s friendship university, 354340, Sochi, Kuibyshev str., 32. E-mail: [email protected]

Fax +7 (8622) 411043

Alfonso Sánchez

Laboratory of Biotechnology, CTAOV. Research Center for Food and Development, CIAD, A.C., Her-mosillo, Sonora 83000, Mexico

N. N. Sazhina

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences 4 Kosygin Street., 119334 Moscow, Russia.

E-mail: [email protected] E-mail: [email protected]

Saleh Shah

Alberta Innovates-Technology Futures, P.O. Bag 4000, Vegreville, Alberta, Canada, T9C 1T4.

A. B. Sharangi

Department of Spices and Plantation Crops, Faculty of Horticulture, Bidhan Chandra Krishi Viswavidya-laya (Agricultural University), Mohanpur, Nadia, WB (INDIA) ,Pin-741252

*Corresponding author: [email protected]

Md. Wasim Siddiqui

Department of Food Science and Technology, Bihar Agricultural University, BAC, Sabour, Bhagalpur, Bi-har (813210) India.

К. P. Skipina

Sochi Institute of Russian people’s friendship university, 354340, Sochi, Kuibyshev str., 32. E-mail: [email protected]

Fax +7 (8622) 411043

Crystal L. Snyder

Carlos Ricardo Soccol

Federal University of Paraná. Dept. Bioprocess and Biotechnology. Rua Francisco H. dos Santos - Centro Politécnico, Jardim das Américas - Curitiba/Pr – Brazil.

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E. A. Soliman

Polymer Materials Research Department, Advanced Technology and New Materials Research Institute, City for Scientific Research and Technological Applications, New Boarg Elarab City, 21934, Alexandria, Egypt.

O. N. Sorokina

Federal state budgetary institution of science Emanuel Institute of Biochemical Physics of Russian Acad-emy of Sciences, Kosygina str., 4, Moscow 119334, Russia.

T. K. Srinivasa Gopal

Central Institute of Fisheries Technology, Cochin, Kerala 628 029.

P Torres-Chavez

Department of Food Research & Graduate Program (DIPA), University of Sonora, Hermosillo, Sonora C.P. 83000, Mexico.

Luciana P. S. Vandenberghe

Randall J. Weselake

G. E. Zaikov

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ACL Admissible concentration limit

AFLP Amplified fragment length polymorphism

AO Antioxidant

AOA Antioxidant activity

AOPs Advanced oxidation processes

AP Active packaging

BAS Biological active substances CAT Capillary agglutination test

CEPM Continuous electrophoresis with porous membranes CFUs Colony forming units

CSNP Chitosan nanoparticles

DDOS Deodorized distillate of soybean oil

DM Dry matter

DSC Differential scanning calorimetry

EITB Enzyme linked immunoelectro transfer blot ELFA Enzyme-linked fluorescent immunoassay ELISA Enzyme-linked immunosorbent assay ES Electrical stimulations

FDA Food and drug administration

FTIR Fourier-transform infrared spectroscopy GAC Granular activated carbon

GC/FID Gas chromatography with flame-ionization detection GC/MS Gas chromatography-mass spectrometry

GFSE Grapefruit seed extract GHP Good hygienic practices GRAS Generally recognized-as-safe

HACCP Hazard analysis of critical control points HOC Halogenated organic compounds

HPLC High-performance liquid chromatography

HS Hard segments

HTC Hard-to-cook

ICGFI International consultative group on food irradiation

IFA Immunofluorescence assay

INIFAP Investigation in forestry, agriculture, and animal production

LA Latex agglutination

LAPS Light-addressable potentiometric sensors MAP Modified atmosphere packaging

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MDSC Modulated differential scanning calorimetry MFE Mercury film electrode

MFI Myofibrillar Fragmentation Index MNPs Magnetic nanoparticles

MWCO Molecular weight cut off PACs Polycyclic aromatic compounds PCR Polymerase chain reaction

PTM Transmembrane pressure

RBPT Rose Bengal plate test ROS Reactive oxygen species

RPLA Reverse passive latex agglutination SEM Scanning electron microscope SEM Scanning electron microscopy SET Staphylococcal enterotoxin TAA Total antioxidant activity

TEAC Trolox equivalent antioxidant capacity TGA Thermogravimetric Analysis

UV Ultraviolet

VLSI Very large scale integration WEAX Water extractable arabinoxylans WHO World Health Organization

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Many foods depend on additives for safety and stability or preservation. Foods are packaged to protect them and keep them in good condition while they are delivered to shops, stacked on shelves, or stored at home. This is a comprehensive advanced level book that provides thorough up-to-date coverage of a broad range of topics in food science and technology and describes avenues of advanced study in the field. The book explores key food commodities and food composition with an emphasis on the functional properties of each commodity.

The so-called HACCP (Hazard Analysis and Critical Control Points) acronym is well known in the food industry in relation to the management of microbiological, chemical, and physical risks. This book is designed to help current and prospective researchers in this field.

This volume introduces and surveys the broad and complex interrelationships among food ingredients and processing, and explores how these factors influence food quality and safety. The book in food science is also a valuable reference for professionals in food processing, as well as for those working in fields that service, regulate, or otherwise interface with the food industry.

This book is divided into 21 chapters:

Thermoplastic polyurethanes bio-based TPUs were synthesized in chapter 1 from a di-functional dimmer fatty acid-based polyol obtained from rapeseed oil, MDI, and BDO at four HS a content that is 10–40 wt%. The polyol characteristics determined the structure and properties of TPUs. The FTIR-ATR spectra confirmed that all the isocyanate groups reacted with hydroxyl groups (from polyol or BDO) during the TPUs synthesis. Thermal studies carried out by TGA, DSC, and MDSC revealed some interactions between hard and soft domains for all TPUs and a degradation behavior closely linked to their HS concentration. Stress-strain uniaxial tests showed that the increase in HS content in TPUs lead to higher tensile modulus and lower elongation at break. The TPU10 and TPU20 showed a strong elastomeric behavior with very high elongation at break (>600%) and very low elastic modulus.

In summary, TPUs partially synthesized from vegetable oils are very promising materials in good agreement with the current tendency for sustainable development, making them very attractive since they are expected to show specific properties which can be easily tailored by selecting the appropriate HS concentration. These materials could also fulfill many industrial requirements for different fields, such as construction, automotive, textile, adhesive, and coatings.

In chapter 2 antioxidant activity of maize bran arabinoxylan micro-spheres were introduced. The comparative analysis of measurements of the total antioxidants content and their activity for juice of 34 different kinds of Kalanchoe (Kalanchoe L.) is carried out by two methods in chapter 3: ammetric and chemiluminescence. Results of

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measurement show good (89%) correlation. Among the studied samples, the two most active kinds of Kalanchoe are exposed: K. scapigera and K. rhombopilosa. They can appear to be more prospective sources of biologically active components in comparison with kinds which are used now. In chapter 4 it is shown that new applications of enzymes within the food industry will depend of the functional understanding of different enzyme classes. Furthermore, the scientific advances in genome research and their exploitation via biotechnology is leading to a technology driven revolution that will have advantages for the consumer and food industry alike. In chapter 5, it is shown that the membranes are among the most important industrial applications today, and every year, more indications are found for this technology, such as water purification, industrial wastewater treatment, dehydration solvent recovery of volatile organic compounds, protein concentration, and many others.

In chapter 6, the various aspects of meat tenderness—such as process of tenderness of meat, practices of meat tenderness, influences of various conditions on meat tenderness, methods of tenderization of meat and meat products and physicochemical determinants of meat tenderness—are discussed. Biological properties of mushrooms are investigated in chapter 7. Molecular and immunological approaches for the detection of important pathogens in foods of animal origin are investigated in chapter 8.

In chapter 9, Cross-Linking of Ferulated Arabinoxylans Extracted from Mexican Wheat Flour: Rheology and Microstructure of the Gel is presented. Free and ester-linked ferulic acid content in a hard-to-cook pinto bean (Phaseolus vulgaris L.) variety is discussed in chapter 10. Chapter 11 discusses polyacrylamide-grafted gelatin: swellable hydrogel delivery system for agricultural applications in detail. The dynamics of bacteria and pathogenic fungi in soil microbiocenosis under the influence of biopreparations used during potato cultivation is introduced in chapter 12.

In chapter 13, the safety of irradiation has been clearly accepted as effective technology, and regulatory authority has been established on a global basis. Consumers’ choice is the final preference for taking the technology to the market. In coming years, irradiation will empower the existing processing technologies. Irradiation is therefore providing safety and health as well as minimizing the losses on a large front and emerging as economical processing as well. Antioxidant properties of various alcohol drinks are studied in chapter 14. A study on the potential of oilseeds as a sustainable source of oil and protein for aquaculture feed is presented in chapter 15. Electrochemical methods for estimation of antioxidant activity of various biological objects are investigated in chapter 16. Ozonolysis of chemical and biochemical compounds are reviewed in chapter 17. Antioxidant activity of mint is explained in chapter 18. Wild orchids of Colchis forests to save them as objects of eco education and as producers of medicinal substances are introduced in chapter 19. Chapter 20 is about the fixation of proteins on MNPs, and chapter 21 studies the antimicrobial packaging for food applications.

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VEGETABLE OILS AS PLATFORM

CHEMICALS FOR SYNTHESIS OF

THERMOPLASTIC BIO-BASED

POLYURETHANES

C. BUENO-FERRER, N. BURGOS, and A. JIMÉNEZ

The use of renewable raw materials constitutes a significant contribution to a sus-tainable development in the plastics production. This strategy is based on the advan-tages given by nature synthesis potential and green chemistry principles. In this sense, polymers obtained from renewable raw materials have raised some interest in the last years. The development of polymers synthesized from agricultural products such as starch, cellulose, sugars, or lignin has been considerably increased in the last two decades [1]. Among all the possible natural sources for polymers, vegetable oils are considered one of the cheapest and abundant in Nature [2]. They can be used as an advantageous chemical platform to polymer synthesis by their inherent biodegradable condition and low toxicity to humans and the environment. In this context, many ef-forts are currently going on to propose a great variety of chemical methods to prepare thermoplastics and thermosets based on vegetable oils. This wide range of chemical methods applicable to these natural materials gives rise to many different monomers and polymers with many applications.

Fatty acids are the major chemical entities present in vegetable oils. They are valu-able compounds to design specific monomers in the search of polymers with particular properties without any need of important modifications in their native structure. This is an advantageous issue not only in sustainability terms but also in industrial applicabil-ity and competitiveness in terms of cost and properties [2-5].

The vegetable oils are mainly formed by triglycerols or triglycerides, mainly com-posed by three fatty acids bonded to a glycerol molecule. Fatty acids constitute 94– 96% of the total triglycerides weight in a vegetable oil and the number of carbon units in their structure is normally between 14 and 22 with zero to three double bonds by fatty acid molecule. The contents in fatty acids in some of the most common vegetable oils are indicated in Table 1.

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TABLE 1

Fatty acid distribution in vegetable oils (g fatty acid/100 g o

il) Fatty acid C:DB Cotton Rapeseed Sunflower Linseed Corn Olive Palm Castor Soybean Myristic 14:0 0.7 0.1 0.0 0.0 0.1 0.0 1.0 0.0 0.1 Myristoleic 14:1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Palmitic 16:0 21.6 4.1 6.1 5.5 10.9 13.7 44.4 1.5 11.0 Palmitoleic 16:1 0.6 0.3 0.0 0.0 0.2 1.2 0.2 0.0 0.1 Stearic 18:0 2.6 1.8 3.9 3.5 2.0 2.5 4.1 0.5 4.0 Oleic 18:1 18.6 60.9 42.6 19.1 25.4 71.1 39.3 5,0 23.4 Linoleic 18:2 54.4 21.0 46.4 15.3 59.6 10.0 10.0 4.0 53.2 Linolenic 18:3 0.7 8.8 1.0 56.6 1.2 0.6 0.4 0.5 7.8 Ricinoleic 18:1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 87.5 0.0 Arachidic 20:0 0.3 0.7 0.0 0.0 0.4 0.9 0.3 0.0 0.3 Gadoleic 20:1 0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Eicosadienoic 20:2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Behenic 22:1 0.2 0.3 0.0 0.0 0.1 0.0 0.1 0.0 0.1 Erucic 22:1 0.0 0.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Lignoceric 24:0 0.0 0.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 DB/triglyceride 3.9 3.9 4.7 6.6 4.5 2.8 1.8 2.7 4.6

Iodine index (I)

104–1 17 91–108 110–143 168– 204 107– 120 84–86 44–58 82–88 117–143

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The use of fatty acids and vegetable oils either in polymer synthesis or as additives comes from some decades, not only by the raising interest in the search for alternatives to fossil fuels but also by the particular chemical characteristics, that make them ad-equate for polymerization processes. Triglycerides are molecules with low reactivity and this fact is a disadvantage in their potential application in polymer synthesis. Nev-ertheless, the introduction of different functionalities in their reactive sites increases largely the synthetic possibilities of triglycerides [3].

At least three different uses of vegetable oils in polymer formulations can be pro-posed:

(i) As polymer additives (plasticizers, stabilizers, and so on), (ii) As building blocks to get polymers from them, and (iii) As units for the thermosets synthesis.

Much work on the use of vegetable oils as additives [6-11] and as thermosets precursors [12-18] has been reported but the development of thermoplastic polymer matrices is still in an early stage of research. Thermoplastics can be easily processed and recycled giving them possibilities in many different applications.

The synthesis of thermoplastics from vegetable oils is still in an early stage of the study and development because of the experimental difficulties to be afforded to get reasonable yields in this process. It is known that thermosets obtained from vegetable oils have been largely studied with many reported work [12-22]. This fact is partially due to the own composition of vegetable oils formed by triglycerides containing dif-ferent fatty acids with variable number of chain instaurations. Thus, seeds oils are rich in polyunsaturated fatty acids giving highly reticulated rigid and temperature resistant materials [21]. The carbon chains forming the oils can be easily cross-linked by their double bonds. As indicated in Table 1, it can be concluded that most seed oils have fatty acids with 2 or 3 unsaturated bonds as the main component in their lipid profile, except castor, olive and rapeseed oils, which show a monounsaturated fatty acid as their main component. Therefore, thermosets can be easily synthesized from oils rich in polyunsaturated fatty acids, such as those from soya, sunflower or linseed getting polymers with high mechanical and thermal resistance. Castor oil shows high content in ricinoleic acid (87.5% in total oil weight) and the active site is occupied by an alco-hol while olive and rapeseed oils show a main content in monounsaturated oleic acid (71.1% and 60.9% in total oil weigh, respectively).

It is known that the potential monomers or polymer building blocks should have at least one (in the case of addition polymerization) or two double bonds in their structure (in the case of condensation polymerization) to get thermoplastic materials. Therefore, triglycerides should be modified of functionalized before polymerization. Neverthe-less, there are some examples of thermoplastic biomaterials obtained from naturally functionalized castor oil with homogeneous composition and acceptable polymeriza-tion yields. The main thermoplastic materials already synthesized from vegetable oils are thermoplastic polyurethanes (TPUs), polyamides (PA), thermoplastic polyesters, polyesteramides, and polyanhidrides.

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1.1.1 TPUS: CHEMISTRY, STRUCTURE, AND PROPERTIES

Polyurethanes are generally synthesized by addition polymerization between a poly-alcohol and a poly-isocyanate. This is an exothermic reaction caused by the release of a proton from the alcohol group followed by a general molecular rearrangement by the formation of the urethane bond. [23]. If both reagents are bi-functional linear polyurethanes are obtained, while if functionalities are increased some cross-linked chains are formed, with the formation of reticulated structures. In summary, one of the most common synthesis routes for TPUs consists basically of the reaction of three main components.

1. Polyols with polyester or polyether functionalities with hydroxyl end groups 2. Di-isocyanate

3. Short-chain diol or diamine used as chain extender

The clear differences in the structure of all these components are essential to get the final properties of the synthesized thermoplastic polyurethanes. The TPUs are block copolymers with (AB)n segmented structure formed by hard and soft blocks.

Soft segments correspond to the elastomeric part of the polymer (polyester chains from the polyol) and they are characterized by a glass transition temperature much lower than ambient which gives them high flexibility. This is the reason why these parts of the polyurethane are known as the soft block. On the other hand, hard seg-ments (HS) are formed by the di-isocyanate and the chain extender forming a rigid structure, mainly formed by the urethane group bonded to aromatic rings. Therefore, some heterogeneity between both blocks in polyurethanes, the HS (with high polar-ity and melting point) and the soft segment (nonpolar and low melting point), should be expected, leading to phase separation in the copolymer structure, as presented in Figure 1 [24,25].

However, the phase separation is not complete in TPUs at the molecular scale, and it is possible to find soft segments inside the hard region and vice-versa (Figure 2), as was reported by Tawa et al. [26]. They indicated that urethane groups from neighbor chains could form hydrogen bonds very easily. These intermolecular bonding leads to the formation of aggregates acting as physical reticulation nodes with crystalline regions dispersed into the soft area in the polymer structure. This would lead to cross-linking with the final result of the increase in the overall rigidity in the TPU. The phase separation between hard and soft segments depends on, among other factors, their affinity, their relative mobility, the chain extender and the isocyanate structural symmetry [25].

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FIGURE 1 Segmented structure of a thermoplastic polyurethane.

FIGURE 2 Polyurethane biphasic structure at molecular scale [26], with permission.

The TPU structures are generally linear, since, the relative amount of HS is small. Therefore, the most relevant properties of these polymers are conditioned by the sec-ondary and intermolecular interactions (mainly Van der Waals) between the soft seg-ments [24,27]. The elastic properties of polyurethanes mainly depend on the polyol chains mobility which is dependent on their chemical nature and length of the soft

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segments. The higher the molar mass of the soft segments the higher tensile strength and elongation to break and consequently the more flexible TPU [24,25].

On the other hand, when the HS content is high, the plastic deformation and the polymer general softening are observed after the application of mechanical stresses at high temperature. The thermal stability of polyurethanes is determined by the temper-ature range where the rigid segments start to melt and consequently their phase sepa-ration and segmented structure. Polyurethanes will show thermoplastic behavior at higher temperatures than the melting point of the hard regions [28]. Another important feature of the hard/soft ratio in TPUs is the decrease of molar masses and low phase separation in polymers with high values of that ratio, conditioning their rheological and mechanical properties, giving rise to more rigid materials. In addition, the isocya-nate structure also influences the final TPU properties. High volume di-isocyaisocya-nates lead to polyurethanes with high elastic modulus and tensile strength [25].

The development of TPUs from vegetable oils is the main goal of this study. In the chapter, some work performed by research group for TPUs synthesized from rapeseed oil dimer fatty acids is presented.

1.2 EXPERIMENTAL DETAILS

1.2.1 MATERIALS

The bio-based polyester polyol used in this study was kindly supplied by Croda (Yorkshire, UK) and it is based on dimmer fatty acids from rapeseed oil with purity higher than 98% and weight average molar mass (M_w) around 3000 g mol–1_{. Hydroxyl}

and acid values are 40 mg KOH g–1_{and 0.253 mg KOH g}–1_{respectively, as given}

by the supplier. 4,4’-diphenylmethane di-isocyanate (MDI) was supplied by Brenntag (Rosheim, France). The 1,4-butanediol (BDO), dibutylamine, toluene, and hydrochlo-ric acid were purchased from Sigma Aldhydrochlo-rich (Lyon, France). All reagents were used without any further purification step.

1.2.2 THE TPU SYNTHESIS

Four different TPUs were prepared with a NCO/OH ratio equal to 1 and increasing HS content (10–40 wt%, named TPU10–TPU40, respectively) by the two-step prepoly-mer process for TPU polyprepoly-merization (Table 2). In a first step, the polyol reacted with an excess of MDI (ratio 2:1) for 2 hr in a five necked round bottom flask having the provision for nitrogen flushing, mechanical stirring, and temperature control at 80°C. During the synthesis, samples were extracted each 30 min in triplicate and diluted in 20 mL of a standard solution of dibutylamine 0.05 M in toluene for the reaction between the residual di-isocyanate and the amine, to control the NCO consumption during the reaction. Each solution was then stirred at room temperature for 10 hr to ensure the complete reaction of NCO groups with dibutylamine. The excess amine was titrated back with standard aqueous HCl 0.05 M solution using bromophenol green as indica-tor. For each titration, 25 mL of isopropyl alcohol were added to the solution to ensure compatibility between dibutylamine and the HCl solution. It was calculated from these

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experiments that 56.1% of NCO groups were consumed at the end of the prepolymer synthesis. This result was used for the addition of the precise amount of diol groups in the processing step. The prepolymer was further melt blended in a second step by reactive processing with the adequate amount of polyol and chain extender, depending on the HS content targeted in the final TPUs. The prepolymer synthesized in the first step and the calculated amount of polyol for a NCO/OH = 1 ratio were directly intro-duced in the feeding zone of an internal mixer (counter-rotating mixer Rheocord 9000, Haake, USA) equipped with a pair of high shear roller type rotors, at 80°C, with a rota-tion speed of 50 rpm and 15 min processing time. Then, the adequate amount of BDO chain extender was added and the temperature was immediately increased to 180°C for 8 min without any catalyst. After polymerization, all systems were cured overnight in an oven at 70°C to ensure the complete reaction of NCO groups which was further checked by attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR). The TPUs were subsequently compression molded in a hot press at 200°C by applying 200 MPa pressure for 5 min and further quenched between two steel plates for 10 min to obtain sheets with 1.5 mm thickness for each system. The expected HS length for each TPU sample was calculated from data in Table 2 by following a proto-col already described by Petrovic et al. [29] to determine the average polymerization degree in segmented polyurethanes. This method was applied to the TPUs synthesized in this study resulting in an HS average polymerization degree of 5–7, 7–9, 11–13, and 19–21 units for TPU10, TPU20, TPU30, and TPU40, respectively. These results could give an estimation of the length of HS for each TPU.

TABLE 2 Calculated HS percentage and reactants amounts for each TPU blend [30], with

permission

Sample HS (wt%) Polyol (g) MDI (g) BDO (g)

TPU10 10 49.5 5.1 0.36

TPU20 20 44.0 9.1 1.94

TPU30 30 38.5 13.0 3.52 TPU40 40 33.0 16.9 5.11

1.3 MATERIALS CHARACTERIZATION

1.3.1 THE ATR-FTIR SPECTROSCOPY

The ATR-FTIR was used to screen the complete reaction between NCO and OH groups and to evaluate the adequate curing of the TPUs. Infrared spectra were collected on a TA Instruments SDT Q600 (Thermo-Nicolet, New Castle, DE, USA) at a resolution of 4 cm-1_{and 64 scans per run. The ATR accessory was equipped with a germanium}

(n = 4) crystal and it was used at a nominal incidence angle of 45° yielding 12 interval reflections at the polymer surface.

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1.3.2 THERMOGRAVIMETRIC ANALYSIS (TGA)

The four TPU systems as well as the bio-based polyol were analyzed in dynamic mode by using TGA/SDTA 851e Mettler Toledo (Schwarzenbach, Switzerland) equipment. Approximately, 7 mg samples were weighed in alumina pans (70 μL) and they were heated from 30ºC to 700°C at 10°C min–1_{under nitrogen atmosphere (flow rate 30 mL}

min–1_{). In the case of TPUs, the initial degradation temperature was calculated as the}

temperature where 5 wt% of the initial mass was lost (T5%). 1.3.3 DIFFERENTIAL SCANNING CALORIMETRY (DSC)

The thermal and structural characterization of TPUs and the polyol was carried out by using a TA Instruments Q2000 (New Castle, DE, USA) equipment. Approximately, 5 mg of each sample were weighed in aluminum pans (40 µL) and they were subjected to a first heating stage from 30ºC to 240ºC with a further cooling from 240ºC to –90ºC and a subsequent heating from –90ºC to 240ºC. All steps were carried out at 10ºC min–1_{under nitrogen (flow rate 50 mL min}–1_{). All tests were performed in duplicate.}

Glass transition temperatures (Tg) were determined on the second heating scan. The

Tg of the polyol was determined by using modulated differential scanning calorimetry

(MDSC) during a cooling scan from 30ºC to –90ºC at 2ºC min–1_{, with 60 sec period}

and heat only mode.

1.3.4 UNIAXIAL MECHANICAL TESTS

Tensile properties of TPUs were determined with an Instron tensile testing machine (model 4204, USA), at 25ºC and 50% relative humidity at a rate of 20 mm min–1_{, using}

dumbbell specimens (dimensions: 30 × 10 × 1.5 mm3_{). For each formulation at least}

five samples were tested.

1.4 DISCUSSION AND RESULTS

1.4.1 THE ATR-FTIR SPECTROSCOPY

The adequate curing of all TPUs is a key point prior to the materials characterization, since the presence of residual NCO groups in the final polymer gives an indication of an incomplete synthesis. In this work, ATR-FTIR was used to confirm the complete reaction between NCO and OH groups. The TPUs spectra are shown in Figure 3 and they could be used to highlight the main structural differences between them. No peak was found at 2270 cm–1_{(NCO stretching band) suggesting that the reaction was}

com-plete in all cases. As expected, the main variations are related to the increasing content in HS and consequently, the higher concentration in urethane groups (-NH-CO-O). In Figure 3, vibrations at 3335 and 1550 cm–1_{corresponded to -NH stretching and}

bend-ing, respectively. Besides, the peak for the C=O stretching from the urethane group could be observed at ≈1700 cm–1_{[31-33]. All these bands, assigned to the urethane}

groups, increased in their intensity from TPU10 to TPU40, with confirmation of the higher concentration in carbonate groups at higher HS contents. Nevertheless, the

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ab-sorption band at 1735 cm–1_{was assigned to the C=O group stretching in the polyol,}

and it was similar for all TPUs, except for TPU10 where this band was broader and almost no discernible from the band at 1700 cm–1_{, certainly due to the lower content in}

urethane groups in this material.

FIGURE 3 The ATR-FTIR spectra of TPU 10–40 wt% of HS and main peak assignments

(cm–1_{) [30] with permission.}

1.4.2 THERMOGRAVIMETRIC ANALYSIS (TGA)

The thermal stability of the polyol and all bio-based TPUs were studied by dynamic TGA. Figure 4 shows their mass losses and derivative curves. The bio-based polyol showed a narrow derivative peak (Figure 4 (b), left) due to its purity, while Figure 4 (b) (right) clearly shows the derivative curves of TPUs with lower intensity peaks. It is known that degradation of polyurethanes is a complex and multistep process, as ob-served in Figure 4. An important parameter, the degradation onset, is dependent on the thermal stability of the less thermally stable part on the polyurethane chains [34,35]. Initial degradation temperatures (T5%) of each step were also studied in TPUs and,

to-gether with mass loss percentages, allowed to study the differences between samples depending on their HS content. It was noted that the T5% value of the pure rapeseed

oil-based polyol was higher than in the case of TPU systems, as it was expected, but also higher than the T5% value reported for castor oil [36] and cashew nut shell

liquid-based polyols [37]. The TPUs also showed higher thermal stability than polymers with similar structures [38]. It has been reported that their first degradation stage is related

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to urethane bond decomposition into isocyanate and alcohol with possible formation of primary and secondary amines [39,40]. Nevertheless, the complexity of this stage is also related with the HS content. In this way, when this content increases T_5% de-creases, making those materials more susceptible to degradation and suggesting that the starting point of degradation takes place predominantly within HS.

FIGURE 4 The TGA curves for mass loss (a) and derivative (b) versus temperature for

bio-based polyol and TPUs [41] with permission.

1.4.3 DIFFERENTIAL SCANNING CALORIMETRY (DSC)

The structure of TPU samples was investigated by DSC while the bio-based polyol was studied both by DSC and MDSC. The main results of this study are shown in Table 3 and Figure 5. This technique is valuable for a precise determination of T_g and from these values it is possible to estimate the real amounts of HS in the unorganized and organized microphases. It has been indicated that HS in TPUs do not fully belong to the hard domains, since, some of them can be found in the soft regions and vice

versa. Moreover, when MDI is not bonded to the chain extender but to the polyol,

presumably in systems with high polyol amount [42], such as in the case of TPU10, this trend is more clearly observed. This phenomenon was also clearly evidenced in the thermal stability of the TPUs, since, the initial degradation temperatures (T_5%) of TPU30 and TPU40 fell significantly with respect to those obtained for TPU10 and TPU20. This behavior could be associated to the higher HS content. Moreover, it

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should be mentioned that the mass loss associated with this first degradation stage could be also correlated with the HS content. In samples with higher HS content, such as TPU30 and TPU40, a peak and a shoulder in their derivative curves were observed, both associated with the first stage of the thermal decomposition of urethane bonds (Figure 4 (b)).

TABLE 3 Glass transition temperatures (Tg) and HS content (%) for TPUs

Sample Tgs SS (ºC) Tgh HS (ºC)

TPU10 –47.0 ---TPU20 –47.8 122.8 TPU30 –50.0 120.7 TPU40 –51.3 118.1

In a preliminary step the bio-based polyol was studied by conventional DSC but the glass transition was not clearly observed since some melting transitions were su-perposed in this temperature range, probably associated to the crystalline polymor-phism of some oils and fats, such as the case of rapeseed oil. Modulation of DSC data (MDSC) is a powerful tool to separate transitions and to get higher resolutions in particular thermal events. In the case of the polyol, MDSC was used during the cooling cycle and the Tg transition was determined in the reversing phase curve at –61.8ºC. It

was also observed that glass transition temperatures of the SS for all TPUs were higher than that of the polyol (Table 3). The Tg values of SS were slightly lower with

increas-ing HS concentrations as it was reported by Xu et al. [43]. Soft domains have higher mobility when larger HS are present and this fact could be related with a better micro-phase separation at high HS content. Besides, the TPUs with lower molar masses and the highest concentrations in HS could contribute to the decrease in Tg values. Higher

amount of end chains could result in higher free volume increasing the mobility of the amorphous phase. Moreover, as it is shown in Figure 5, Tg transition of the MDI-BDO

HSs was very difficult to detect due to their stiffness and low mobility [42]. The Tg of

HS of TPUs slightly increased when their concentration decreased. This result could be attributed to the higher concentration in HS inside the soft domains as explained. Moreover, the intensity of the glass transition of HS is larger at higher HS content but the Tg value is lower, suggesting some interactions between hard and soft phases, that

is the low Tg of SS observed for TPU40 which was previously attributed to the

micro-phase separation, could also help to the decrease in Tg of HS in this material due to the

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FIGURE 5 The DSC curves from TPU samples and zoom in the zone of Tg of HS [30] with

permission.

1.4.4 UNIAXIAL MECHANICAL TESTS

Tensile properties were determined by uniaxial tensile tests and data are summarized in Table 4 and Figure 6. Results showed that the increase in HS content lead to a brittle material with higher tensile modulus and lower elongation at break (around 25% for TPU40), as expected, while this material showed lower tensile strength than TPU30 and TPU20. This behavior could be attributed to the fragility provided by the crystalline macro-structures with sizes between 20 and 30 μm that were observed in a morphological study [30]. The presence of these macro-structures in TPU40 increased the segregation phase size and may promote points of stress concentration, due to their boundary impingement, which could influence properties such as tensile strength and elongation at break [43]. As expected, TPU40 also exhibited the higher modulus (11.1 MPa), leading to the conclusion that the HS higher crystallinity has a significant effect on the mechanical properties of these TPUs.

TABLE 4 Uniaxial tensile properties of TPUs [41] with permission

Sample Tensile Strength (MPa) Elongation at Break (%) Young Modulus (MPa) TPU10 1.3 ± 0.1 >600 0.7 ± 0.0

TPU20 3.7 ± 0.1 >600 2.5 ± 0.1

TPU30 5.6 ± 0.3 430 ± 40 8.6 ± 0.5

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Figure 6 shows the elastomeric behavior of those TPUs with lower HS content as demonstrated by their lower moduli. It was also observed in Figure 6 that TPU20 was the only material with a yield point in the range of deformation 250–300%. This par-ticular behavior, presented as a rubbery region in Figure 6, could be related to a good resistance to the permanent deformation.

FIGURE 6 Stress-strain curves of TPUs [41] with permission.

1.5 CONCLUSION

Bio-based TPUs were synthesized from a di-functional dimmer fatty acid-based polyol obtained from rapeseed oil, MDI, and BDO at four HS contents that is 10–40 wt%. The polyol characteristics determined the structure and properties of TPUs. The FTIR-ATR spectra confirmed that all the isocyanate groups reacted with hydroxyl groups (from polyol or BDO) during the TPUs synthesis. Thermal studies carried out by TGA, DSC, and MDSC revealed some interactions between hard and soft domains for all TPUs and a degradation behavior closely linked to their HS concentration. Stress-strain uniaxial tests showed that the increase in HS content in TPUs lead to higher tensile modulus and lower elongation at break. The TPU10 and TPU20 showed a strong elastomeric behavior with very high elongation at break (>600%) and very low elastic modulus.

In summary, TPUs partially synthesized from vegetable oils are very promising materials in good agreement with the current tendency for sustainable development and making them very attractive since they are expected to show specific properties which can be easily tailored by selecting the appropriate HS concentration. These materials could also fulfill many industrial requirements for different fields such as construction, automotive, textile, adhesive, and coatings.

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KEYWORDS

• Bio-based polyols • Dimmer fatty acids • Hard segment distribution • Polyurethanes

• Structure-property relationships

ACKOWLEDGMENT

Authors thank the Spanish Ministry of Economy and Competitiveness (MAT2011-28648-C02-01) for financial support.

REFERENCES

1. Lligadas, G., Ronda, J. C., Galià, M., and Cádiz, V. Plant Oils as Platform Chemicals for Polyurethane Synthesis: Current-State-of-the-Art. Biomacromolecules, 11, 2825–2835 (2010).

2. Biermann, U., Friedt, W., Lang, S., Luhs, W., Machmuller, G., Metzger, J. O., Klaas, M. R. G., Schafer, H. J., and Scheider, M. P. New Syntheses with Oils and Fats as Renewable Raw Materials for the Chemical Industry. Angewandte Chemie International Edition, 39, 2206–2224 (2000).

3. Montero de Espinosa, L. and Meier, M. A. R. Plant oils: The perfect renewable resource for polymer science?, European Polymer Journal, 47, 837–852 (2011).

4. Behr, A. and Gomes, J. P. The refinement of renewable resources: New important de-rivatives of fatty acids and glycerol. European Journal of Lipid Science and Technology,

112(1), 31–50 (2010).

5. Kockritz, A., Khot, S. N. M., Lascala, J. J., Can, E., Morye, S. S., Williams, G. I., Palmese, G. R., Kusefoglu, S. H., and Wool, R. P. Development and application of triglyceride-based polymers and composites. Journal of Applied Polymer Science, 82(3), 703–723 (2001).

6. Benaniba, M. T., Belhaneche-Bensemra, N., and Gelbard, G. Stabilizing effect of epoxi-dized sunflower oil on the thermal degradation of poly(vinyl chloride). Polymer

Degrada-tion and Stability, 74, 501–505 (2001).

7. Boussoum, M. O., Atek, D., and Belhaneche-Bensemra, N. Interactions between poly(vinyl chloride) stabilised with epoxidised sunflower oil and food simulants. Polymer

Degrada-tion and Stability, 91, 579–584 (2006).

8. Choi, J. S. and Park, W. H. Thermal and mechanical properties of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) plasticized by biodegradable soybean oils. Macromolecular

Sym-posium, 197, 65–76 (2003).

9. Semsarzadeh, M. A., Mehrabzadeh, M., and Arabshahi, S. S. Mechanical and Thermal Properties of the Plasticized PVC-ESBO. Iranian Polymer Journal, 14(9), 769–773 (2005).

10. Ali, F., Chang, Y. W., Kang, S. C., and Yoon, J. Y. Thermal, mechanical, and rheological properties of poly(lactic acid)/epoxidized soybean oil blends. Polymer Bulletin, 62(1), 91–98 (2009).

(35)

11. Karmalm, P., Hjertberg, T., Jansson, A., and Dahl, R. Thermal stability of poly(vinyl chlo-ride) with epoxidised soybean oil as primary plasticizer. Polymer Degradation and

Stabil-ity, 94, 2275–2281 (2009).

12. Meier, M. A. R., Metzger, J. O., and Schubert, U. S. Plant oil renewable resources as green alternatives in polymer science. Chemical Society Reviews, 36, 1788–1802 (2007). 13. Güner, F. S., Yagci, Y., and Erciyes, A. T. Polymers from trygliceride oils. Progress in

Polymer Science, 31, 633–670 (2006).

14. Lu, Y. and Larock, R. C. Novel polymeric materials from vegetable oils and vinyl mono-mers: Preparation, properties, and applications. ChemSusChem, 2(2), 136–147 (2009). 15. Khot, S. N., Lascala, J. J., Can, E., Morye, S. S., Williams, G. I., Palmese, G. R.,

Kuse-foglu, S. H., and Wool Development and application of triglyceride-based polymers and composites. Journal of Applied Polymer Science, 82(3), 703–723 (2001).

16. Hablot, E., Zheng, D., Bouquey, M., and Averous, L. Polyurethanes Based on Castor Oil: Kinetics, Chemical, Mechanical, and Thermal Properties. Macromolecular Materials and

Engineering, 293(11), 922–929 (2008).

17. Liu, Z. and Erhan, S. Z. “Green” composites and nanocomposites from soybean oil.

Mate-rials Science and Engineering A, 483–484, 708–711 (2008).

18. Doll, K. M. and Erhan, S. Z. The improved synthesis of carbonated soybean oil using su-percritical carbon dioxide at a reduced reaction time. Green Chemistry, 7, 849–854 (2005). 19. Meiorin, C., Aranguren, M. I., and Mosiewicki, M. A. Smart and structural thermosets

from the cationic copolymerization of a vegetable oil. Journal of Applied Polymer

Sci-ence, 124(6), 5071–5078 (2011).

20. Kong, X., Omonov, T. S., and Curtis, J. M. The development of canola oil based bio-resins. Lipid Technology, 24(1), 7–10 (2012).

21. Kim, J. R. and Sharma, S. The development and comparison of bio-thermoset plastics from epoxidized plant oils. Industrial Crops and Products, 36(1), 485–499 (2012). 22. Quirino, R. L., Woodford, J., and Larock, R. C. Soybean and linseed oil-based composites

reinforced with wood flour and wood fibers. Journal of Applied Polymer Science, 124(2), 1520–1528 (2012).

23. Seymour, R. B. and Carraher, C. E. Polymer Chemistry - An introduction. 2nd Edition. Marcel Dekker, Basel, Suiza (1988).

24. Ionescu, M. Chemistry and Technology of Polyols for Polyurethanes. Rapra Technology Limited, Shropshire, United Kingdom (2005).

25. Meier-Westhues, U. Polyurethanes. Coatings, adhesives, and sealants. Vincentz Network, Hannover, Alemania (2007).

26. Tawa, T. and Ito, S. The role of hard segments of aqueous polyurethane-urea dispersion in determining the colloidal characteristics and physical properties. Polymer Journal, 38(7), 686–693 (2006).

27. Wool, R. P. and Sun, X. S. Bio-Based Polymers and Composites. Elsevier Academic Press, Burlington, MA, United States (2005).

28. Yamasaki, S., Nishiguchi, D., Kojio, K., and Furukawa, M. Effects of Polymerization Method on Structure and Properties of Thermoplastic Polyurethanes. Journal of Polymer

Science B: Polymer Physics, 45, 800–814 (2007).

29. Petrovic, Z. S., Cevallos, M. J., Javni, I., Schaefer, D. W., and Justice, R. Soy-oil-based segmented polyurethanes. Journal of Polymer Science B, 43, 3178–3190 (2005).

30. Bueno-Ferrer, C., Hablot, E., Perrin-Sarazin, F., Garrigós, M. C., Jiménez, A., and Avé-rous, L. Structure and morphology of new bio-based thermoplastic polyurethanes obtained from dimer fatty acids. Macromolecular Materials and Engineering, 297(8), 777–784 (2012).

(36)

31. Irusta, L. and Fernandez-Berridi, M. J. Aromatic poly(ester–urethanes): effect of the poly-ol mpoly-olecular weight on the photochemical behaviour. Ppoly-olymer, 41, 3297–3302 (2000). 32. Irusta, L., Iruin, J. J., Mendikute, G., and Fernández-Berridi, M. J. Infrared spectroscopy

studies of the self-association of aromatic urethanes. Vibrational Spectroscopy, 39, 144– 150 (2005).

33. Silva, B. B. R., Santana, R. M. C., and Forte, M. M. C. A solvent less castor oil-based PU

adhesive for wood and foam substrates. International Journal of Adhesion and

Adhe-sives, 30, 559–565 (2010).

34. Javni, I., Petrovic, Z., Guo, A., and Fuller, R. Thermal stability of polyurethanes based on vegetable oils. Journal of Applied Polymer Science, 77, 1723–1734 (2000).

35. Król, P. Synthesis methods, chemical structures and phase structures of linear polyure-thanes. Properties and applications of linear polyurethanes in polyurethane elastomers, copolymers and ionomers. Progress in Materials Science, 52, 915–1015 (2007).

36. Corcuera, M. A., Rueda, L., Fernandez d’Arlas, B., Arbelaiz, A., Marieta, C., Mondragon, I., and Eceiza, A. Microstructure and properties of polyurethanes derived from castor oil.

Polymer Degradation and Stability, 95, 2175–2184 (2010).

37. Bhunia, H. P., Nando, G. B., Chaki, T. K., Basak, A., Lenka, S., and Nayak, P. L. Synthe-sis and characterization of polymers from cashewnut shell liquid (CNSL), a renewable resource II. Synthesis of polyurethanes. European Polymer Journal, 35, 1381–131 (1999). 38. Yeganeh, H. and Mehdizadeh, M. R. Synthesis and properties of isocyanate curable mill-able polyurethane elastomers based on castor oil as a renewmill-able resource polyol. European

Polymer Journal, 40, 1233–1238 (2004).

39. Hablot, E., Zheng, D., Bouquey, M., and Avérous, L. Polyurethanes based on castor oil: kinetics, chemical, mechanical and thermal properties. Macromolecular Materials and

Engineering, 293, 922–929 (2008).

40. Hojabri, L., Kong, X., and Narine, S. S. Fatty acid-derived diisocyanate and biobased polyurethane produced from vegetable oil: synthesis, polymerization and characterization.

Biomacromolecules, 10, 884–891 (2009).

41. Bueno-Ferrer, C., Hablot, E., Garrigós, M. C., Bocchini, S., Avérous, L., and Jiménez, A. Relationship between morphology, properties and degradation parameters of novative bio-based thermoplastic polyurethanes obtained from dimer fatty acids. Polymer Degradation

and Stability, 97(10), 1964–1969 (2012).

42. Bagdi, K., Molnar, K., Pukanszky, Jr. B., and Pukanszky, B. Thermal analysis of the struc-ture of segmented polyurethane elastomers. Journal of Thermal Analysis and Calorimetry,

98, 825–832 (2009).

43. Xu, Y., Petrovic, Z., Das, S., and Wilkes, G. L. Morphology and properties of thermoplas-tic polyurethanes with dangling chains in ricinoleate-based soft segments. Polymer, 49, 4248–4258 (2008).

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Food Composition and Analysis - Methods and Strategies (2014)

Food Composition and Analysis

Methods and Strategies

FOOD COMPOSITION and ANALYSIS

Methods and Strategies

Haghi

Millan

Methods and Strategies

FOOD COMPOSITION and ANALYSIS

Methods and Strategies

Haghi

Millan

H C

CH

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CH

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Food Composition and Analysis

Methods and Strategies

Apple Academic Press

Methods and Strategies

and

ANALYSIS

FOOD COMPOSITION

Editors

PhD

PhD

A. K. Haghi,

Elizabeth Carvajal-Millan,

Methods and Strategies

and

ANALYSIS

FOOD COMPOSITION

Editors

PhD

PhD

A. K. Haghi,

Elizabeth Carvajal-Millan,

FOOD COMPOSITION

AND ANALYSIS

FOOD COMPOSITION

AND ANALYSIS

Methods and Strategies

Apple Academic Press

VEGETABLE OILS AS PLATFORM

CHEMICALS FOR SYNTHESIS OF

THERMOPLASTIC BIO-BASED

POLYURETHANES

CONTENTS