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UNIVERSITAT ROVIRA I VIRGILI POLYBENZOXAZINE MATERIALS FROM RENEWABLE DIPHENOLIC ACID Camilo Javier Zúñiga Ruiz Dipòsit Legal: T.1559-2013 Camilo Javier Zúñiga Ruiz POLYBENZOXAZINE MATERIALS FROM RENEWABLE DIPHENOLIC ACID PhD thesis Supervised by Dr. Virginia Cádiz Deleito and Dr. Joan Carles Ronda Bargalló Department of Analytical Chemistry and Organic Chemistry Tarragona 2013 UNIVERSITAT ROVIRA I VIRGILI POLYBENZOXAZINE MATERIALS FROM RENEWABLE DIPHENOLIC ACID Camilo Javier Zúñiga Ruiz Dipòsit Legal: T.1559-2013 UNIVERSITAT ROVIRA I VIRGILI POLYBENZOXAZINE MATERIALS FROM RENEWABLE DIPHENOLIC ACID Camilo Javier Zúñiga Ruiz Dipòsit Legal: T.1559-2013 Depaartament de Química Analítica i Química Orgànica C/ Marcel·lí Domingo, s/n Campus Sescelades 43007, Tarragona Telf. 977 559 769 Fax. 977 558 446 Virginia Cádiz Deleito y Joan Carles Ronda Bargalló, ambos catedráticos del Departamento de Química Analítica y Química Orgánica de la Universidad Rovira i Virgili, HACEN CONSTAR que la presente tesis doctoral, titulada “Polybenzoxazine materials from renewable dipphenolic acid” presentada ppor Camilo Javier Zúññiga Ruiz para la obtención del título de Doctor, ha sido realizada bajo nuestra dirección en el Departamento de Química Annalítica y Química Orgánica de esta Universidad y que cumple con los requisitos para poder optar a la Mención Europea Tarragona, 23 de julio de 2013 Dra. Virginia Cádiz Dr. Joan Carles Ronda UNIVERSITAT ROVIRA I VIRGILI POLYBENZOXAZINE MATERIALS FROM RENEWABLE DIPHENOLIC ACID Camilo Javier Zúñiga Ruiz Dipòsit Legal: T.1559-2013 UNIVERSITAT ROVIRA I VIRGILI POLYBENZOXAZINE MATERIALS FROM RENEWABLE DIPHENOLIC ACID Camilo Javier Zúñiga Ruiz Dipòsit Legal: T.1559-2013 CONTENTS CHAPTER 1. GENERAL INTRODUCTION AND SCOPE 1 1.1. General introduction 3 1.2. Scope and purpose of the thesis 18 CHAPTER 2. DIPHENOLIC ACID AS PLATFORM CHEMICAL FOR THE 25 SYNTHESIS OF POLYBENZOXAZINE MATERIALS 2.1. Introduction 27 2.2. Flame retardancy in polymers 27 2.2.1. Polymer combustion 28 2.2.2. General flame retardant mechanisms 28 2.2.3. Types of flame retardants 29 2.2.4. Polymer flammability tests 32 2.3. Polybenzoxazine/fiberglass composites 33 2.4. Objectives 35 2.5. Experimental procedures and results 35 2.5.1. Polybenzoxazines from renewable diphenolic acid 39 2.5.2. Renewable polybenzoxazines based in diphenolic acid 61 CHAPTER 3. POLYBENZOXAZINE FOAMS 81 3.1. Introduction 83 3.2. General aspects of foams 83 3.3. Properties of foams 86 3.3.1. Mechanical properties 86 3.3.2. Thermal properties 87 3.4. Types of polymeric foams 87 3.5. Flame retardant foams 88 3.6. Benzoxazine derived foams 90 3.7. Objectives 92 3.8. Experimental procedures and results 92 3.8.1. Self-foaming diphenolic acid benzoxazine 97 UNIVERSITAT ROVIRA I VIRGILI POLYBENZOXAZINE MATERIALS FROM RENEWABLE DIPHENOLIC ACID Camilo Javier Zúñiga Ruiz Dipòsit Legal: T.1559-2013 3.8.2. Phosphorus flame retardant polybenzoxazine foams 115 based on renewable diphenolic acid 3.8.3. Modeling of the foaming process of a phosphorus flame 143 retardant polybenzoxazine CHAPTER 4. MULTI WALLED CARBON NANOTUBES/ 157 POLYBENZOXAZINE NANOCOMPOSITES 4.1. Introduction 163 4.2. Carbon nanotubes 163 4.3. Polymer nanocomposites 165 4.3.1. Fabrication methods of carbon nanotube/polymer 166 composites 4.3.2. Properties of carbon nanotube/polymer composites 166 4.4. Carbon-based/polybenzoxazine nanocomposites 167 4.5. Objectives 168 4.6. Experimental procedures and results 169 4.6.1. Convenient and solventless preparation of neat carbon 173 nanotubes/polybenxozazine nanocomposites with low percolation threshold and improved thermal and fire properties GENERAL CONCLUSIONS 193 APPENDICES 197 Appendix A List of abbreviations 199 Appendix B List of publications 201 Appendix C Meeting contributions and stage 202 UNIVERSITAT ROVIRA I VIRGILI POLYBENZOXAZINE MATERIALS FROM RENEWABLE DIPHENOLIC ACID Camilo Javier Zúñiga Ruiz Dipòsit Legal: T.1559-2013 CHAPTER 1 GENERAL INTRODUCTION AND SCOPE UNIVERSITAT ROVIRA I VIRGILI POLYBENZOXAZINE MATERIALS FROM RENEWABLE DIPHENOLIC ACID Camilo Javier Zúñiga Ruiz Dipòsit Legal: T.1559-2013 UNIVERSITAT ROVIRA I VIRGILI POLYBENZOXAZINE MATERIALS FROM RENEWABLE DIPHENOLIC ACID Camilo Javier Zúñiga Ruiz Dipòsit Legal: T.1559-2013 1.1. GENERAL INTRODUCTION Undoubtedly the diversity of polymers and the flexibility of their properties are employed to produce a broad variety of products that bring medical, technological advances, energy savings and numerous other societal benefits. Plastics are everywhere and although today most plastic items are banal and uninteresting to the user/consumer, a day without their use would be unthinkable. As a result, the global plastics production has increased substantially over the last decades from around 0.5 million tonnes in 1950 to 280 million tonnes in 2011, with an annually increase of 9%1 (Figure 1). Almost all aspects of daily life involve plastics e.g., telecommunications, sports, clothing, footwear and as packing materials that facilitate the transport of a wide of goods. For instance, in Europe the plastic application sector is led by packing (39%), followed by building & construction (20.5%), automotive (8.3%) and electrical & electronic equipment (5.4%) of overall demand. Others (26.4%) include various sectors such as consumer and household appliances, furniture, agriculture, sport, health and safety1. Despite several and well-known benefits of plastics, concerns about usage and final disposal, sustainability, environment and effects on wildlife and humans are gaining momentum in both academic and scientific fields. Usually, plastics are additivated to improve their performance with substantial quantities of one or more chemical compounds. Unfortunately, some of them are toxic or could leach out of products being potentially harmful for humans and wildlife2. On the other hand, around 4% of world oil and gas production, a non-renewable resource, is used as feedstock for plastics and a further 3-4% is expended to provide energy for their manufacture3. Given the depletion of fossil fuels reserves, the dramatic fluctuation in oil prices, and the relationship between the cost/risk to safety, health and the environment, the use of hydrocarbons for producing low-cost plastic with short-lived applications is becoming increasingly not sustainable4. In addition to the reliance on finite resources of plastic production, and concerns about additive effects of chemicals, current patterns of usage are generating global waste management problems. In 2011 post-consumer plastic waste generation across the European Union was 25.1 million tonnes1. Large quantities of plastic debris have been accumulated in the natural environment by contaminating a wide range of natural terrestrial and freshwater ecosystems. UNIVERSITAT ROVIRA I VIRGILI POLYBENZOXAZINE MATERIALS FROM RENEWABLE DIPHENOLIC ACID Camilo Javier Zúñiga Ruiz Dipòsit Legal: T.1559-2013 Without going further, the great pacific garbage patch, a gyre composed of floating waste plastic and other products, is just a simple example of the ill-fated consequences of the accumulation of plastic waste in the natural environment. Apart from the physical problems related to plastic debris, there exist other problems resulting from ingestion and entanglement of debris in wildlife5,6.