Advanced chemistry and physics of polymers
A.A. 2024/2025
Obiettivi formativi
The fundamental learning objective of this course is to provide Students with a clear picture of the fundamental concepts of the synthesis and characterization of polymers useful for addressing the study of advanced monographic courses on polymers. In the first phase of the course, the introductory notions normally provided in the basic courses on polymers will be resumed.
Students will acquire a thorough knowledge of both classical and advanced mechanisms for the synthesis of polymers. Particular emphasis will be given to the controlled syntheses of complex polymeric architectures, including among the latter the controlled radical polymerization and ring-opening polymerization mechanisms.
Students will learn the thermal properties of polymers and their methods of determination.
Students will acquire a global vision of the different methods of determining molecular weights, both classical and advanced.
Students will learn the rheological properties of polymers and the importance of their knowledge for the correct development of the polymer processing stages.
Finally, the basic notions of the mechanical and dynamic-mechanical properties of polymers will be introduced.
Students will acquire a thorough knowledge of both classical and advanced mechanisms for the synthesis of polymers. Particular emphasis will be given to the controlled syntheses of complex polymeric architectures, including among the latter the controlled radical polymerization and ring-opening polymerization mechanisms.
Students will learn the thermal properties of polymers and their methods of determination.
Students will acquire a global vision of the different methods of determining molecular weights, both classical and advanced.
Students will learn the rheological properties of polymers and the importance of their knowledge for the correct development of the polymer processing stages.
Finally, the basic notions of the mechanical and dynamic-mechanical properties of polymers will be introduced.
Risultati apprendimento attesi
At the end of the course, the Student will be able to:
1. Define the basic concepts and terms essential for the study of polymer science.
2. Identify the classes of polymerizable monomers with the synthetic mechanisms described.
3. Describe the fundamental mechanisms used for the synthesis of complex and controlled polymer architectures, in particular using living polymerization mechanisms.
4. Understand the different characteristics of the amorphous and crystalline solid state of polymers and the influence of the transition temperatures typical of these states on the physical properties and workability of the polymers.
5. Interpret simple calorimetric traces of the DSC type, identifying melting and glass transition temperatures and physical aging phenomena.
6. Interpret simple thermogravimetric (TGA) plots to determine the thermal stability of polymers and the composition of polymer blends.
7. Interpret simple MALDI-TOF spectra for the identification of the distribution of the molecular masses of the polymers and their structural details.
8. Interpret simple SEC spectra. For the determination of the molecular weights of polymers.
9. Classify the rheological curves of polymers.
10. Know the basic definitions and constitutive equations that describe the viscoelastic behavior of polymers.
1. Define the basic concepts and terms essential for the study of polymer science.
2. Identify the classes of polymerizable monomers with the synthetic mechanisms described.
3. Describe the fundamental mechanisms used for the synthesis of complex and controlled polymer architectures, in particular using living polymerization mechanisms.
4. Understand the different characteristics of the amorphous and crystalline solid state of polymers and the influence of the transition temperatures typical of these states on the physical properties and workability of the polymers.
5. Interpret simple calorimetric traces of the DSC type, identifying melting and glass transition temperatures and physical aging phenomena.
6. Interpret simple thermogravimetric (TGA) plots to determine the thermal stability of polymers and the composition of polymer blends.
7. Interpret simple MALDI-TOF spectra for the identification of the distribution of the molecular masses of the polymers and their structural details.
8. Interpret simple SEC spectra. For the determination of the molecular weights of polymers.
9. Classify the rheological curves of polymers.
10. Know the basic definitions and constitutive equations that describe the viscoelastic behavior of polymers.
Periodo: Primo semestre
Modalità di valutazione: Esame
Giudizio di valutazione: voto verbalizzato in trentesimi
Corso singolo
Questo insegnamento può essere seguito come corso singolo.
Programma e organizzazione didattica
Edizione unica
Responsabile
Periodo
Primo semestre
Programma
1. Introduction to polymer science
General definitions and classifications of polymers. Plastics and their relevance. Natural, synthetic, artificial, inorganic polymers. Statistical, alternating, block, and graft copolymers and their significance. Geometric isomerism, configurations, and conformations of polymers. The molecular mass of polymers: molecular mass distribution; numerical and weighted average values; polydispersity.
2. Step-wise polymerization mechanism
Polymerizable monomers. Dependence of the polymerization degree on the reaction parameters in the absence and presence of monofunctional monomers; time dependence of the polymerization degree; number and weight distribution functions of molecular masses. Synthesis of cross-linked polymers.
3. Free radical polymerization mechanism (FRP)
Polymerizable monomers. General process features: fast and exothermic reactions; main reaction steps: initiation, propagation, termination, and chain transfer. Dependence of the average polymerization degree on the reaction parameters. Chain transfer: Mark-Houwink-Sukurada equation. Inhibition and retardation reactions. Self-acceleration effect. Depolymerization reaction and "ceiling temperature".
4. Polymerization with ionic mechanisms
Polymerizable monomers; initiators for cationic and anionic mechanisms; solvent dependence of the polymerization rate. Cationic mechanism: chain transfer step; temperature effect on the reaction products. Anionic mechanism: living polymerization.
5. Stereospecific polymerization mechanisms using metallocene catalysts
Polymerizable monomers; composition and structure of metallocene catalysts and their general reactivity. Effect of methylaluminoxanes (MAO). Polymerization through poly-insertion mechanism. Stereospecific control: iso- and syndiospecific catalysts. Effect of the catalyst symmetry.
6. Controlled radical polymerization mechanisms (CRP): nitroxide mediated polymerization (NMP); ATP (atom transfer polymerization); reversible addition-fragmentation transfer (RAFT) polymerization.
7. Ring-opening polymerization (r.o.p.) mechanism: polymerizable monomers. Thermodynamic and kinetic control. Classification of the initiators: electrophilic and nucleophilic ring opening. Polymers of industrial interest. Solvent effect. Classification as a chain-growth or step-wise mechanism. Living polymerization.
8. Group transfer polymerization
9. Analysis of molecular masses: solution properties of polymers. Solution viscosity. Size exclusion chromatography offline and online light scattering. Zimm plot. MALDI-TOF mass analysis.
10. Thermal analysis of polymers: amorphous and crystalline state in polymers. Crystalline polymers: requirements for achieving crystallinity; semi-crystalline polymers; morphology of polymeric crystals (lamellae and spherulites. Amorphous polymers: glass transition temperature, Tg, as a non-thermodynamic transition. Crystallization rate. Scanning calorimetric analysis (DSC): classification of existing instruments and operating principles. Analysis of glass transition temperature and melting temperature. Examples of DSC thermograms. Dependency of the shape of the thermograms on heating and cooling rate. Physical aging and annealing effects. Modulated DSC (MDSC).
11. Thermogravimetric analysis: operating principle and application to the study of the thermal and thermo-oxidative decomposition of polymers. Decomposition temperature onset at different weight loss, and maximum decomposition temperature. Effect of the heating rate and of the sample mass. Analysis of copolymers. Advanced TGA techniques: dynamic (Hi-Res), constant reaction rate, and step-wise isothermal TGA.
12. Rheology of polymers: general definitions and concept of viscoelasticity. Flow curves and flow regimes. Dependence of viscosity on temperature, time, molecular weight, deformation rate, and shear stress.
13. Mechanical and dynamic mechanical properties of polymers. Analysis of the stress-strain curves.
General definitions and classifications of polymers. Plastics and their relevance. Natural, synthetic, artificial, inorganic polymers. Statistical, alternating, block, and graft copolymers and their significance. Geometric isomerism, configurations, and conformations of polymers. The molecular mass of polymers: molecular mass distribution; numerical and weighted average values; polydispersity.
2. Step-wise polymerization mechanism
Polymerizable monomers. Dependence of the polymerization degree on the reaction parameters in the absence and presence of monofunctional monomers; time dependence of the polymerization degree; number and weight distribution functions of molecular masses. Synthesis of cross-linked polymers.
3. Free radical polymerization mechanism (FRP)
Polymerizable monomers. General process features: fast and exothermic reactions; main reaction steps: initiation, propagation, termination, and chain transfer. Dependence of the average polymerization degree on the reaction parameters. Chain transfer: Mark-Houwink-Sukurada equation. Inhibition and retardation reactions. Self-acceleration effect. Depolymerization reaction and "ceiling temperature".
4. Polymerization with ionic mechanisms
Polymerizable monomers; initiators for cationic and anionic mechanisms; solvent dependence of the polymerization rate. Cationic mechanism: chain transfer step; temperature effect on the reaction products. Anionic mechanism: living polymerization.
5. Stereospecific polymerization mechanisms using metallocene catalysts
Polymerizable monomers; composition and structure of metallocene catalysts and their general reactivity. Effect of methylaluminoxanes (MAO). Polymerization through poly-insertion mechanism. Stereospecific control: iso- and syndiospecific catalysts. Effect of the catalyst symmetry.
6. Controlled radical polymerization mechanisms (CRP): nitroxide mediated polymerization (NMP); ATP (atom transfer polymerization); reversible addition-fragmentation transfer (RAFT) polymerization.
7. Ring-opening polymerization (r.o.p.) mechanism: polymerizable monomers. Thermodynamic and kinetic control. Classification of the initiators: electrophilic and nucleophilic ring opening. Polymers of industrial interest. Solvent effect. Classification as a chain-growth or step-wise mechanism. Living polymerization.
8. Group transfer polymerization
9. Analysis of molecular masses: solution properties of polymers. Solution viscosity. Size exclusion chromatography offline and online light scattering. Zimm plot. MALDI-TOF mass analysis.
10. Thermal analysis of polymers: amorphous and crystalline state in polymers. Crystalline polymers: requirements for achieving crystallinity; semi-crystalline polymers; morphology of polymeric crystals (lamellae and spherulites. Amorphous polymers: glass transition temperature, Tg, as a non-thermodynamic transition. Crystallization rate. Scanning calorimetric analysis (DSC): classification of existing instruments and operating principles. Analysis of glass transition temperature and melting temperature. Examples of DSC thermograms. Dependency of the shape of the thermograms on heating and cooling rate. Physical aging and annealing effects. Modulated DSC (MDSC).
11. Thermogravimetric analysis: operating principle and application to the study of the thermal and thermo-oxidative decomposition of polymers. Decomposition temperature onset at different weight loss, and maximum decomposition temperature. Effect of the heating rate and of the sample mass. Analysis of copolymers. Advanced TGA techniques: dynamic (Hi-Res), constant reaction rate, and step-wise isothermal TGA.
12. Rheology of polymers: general definitions and concept of viscoelasticity. Flow curves and flow regimes. Dependence of viscosity on temperature, time, molecular weight, deformation rate, and shear stress.
13. Mechanical and dynamic mechanical properties of polymers. Analysis of the stress-strain curves.
Prerequisiti
Basic knowledge of organic chemistry included in the Organic Chemistry I course of the 1st level degree course (bachelor's degree). These include nomenclature, structure, and general reactivity of aliphatic and aromatic compounds; reactivity of alkenes, alkynes, aliphatic halides, and carboxylic acids; synthesis of esters, amides, urethanes, and urea.
Metodi didattici
Lectures with the aid of slides.
Materiale di riferimento
1. Instructor notes, both as Power Pont files and videos available at https://eranuccipc.ariel.ctu.unimi.it/
2. "Principles of polymerization" Geroge Odian, Wiley.
2. "Principles of polymerization" Geroge Odian, Wiley.
Modalità di verifica dell’apprendimento e criteri di valutazione
The exam will consist of a written test in which students are asked to answer open questions concerning the entire program of the course. The aim is to verify the acquired knowledge and understanding of the concepts discussed during the course. The score will vary from 18 to 30 proportionally to the correctness of the answers.
1. General definitions and introductory concepts on polymer science.
2. Mechanisms of polymer synthesis: families of polymerizable monomers; chain growth steps; chain transfer reactions; conversion dependence of the molecular masses in the various polymerization processes.
3. Discussion of the stereo-control in polymerizations with coordination mechanism.
4. Definitions and characteristics of the solid state of polymers.
5. Knowledge of the main values of the glass transition and melting temperatures of the commercial polymers mentioned during the course.
6. Thermo-analytical methods: main experimental methods and their applications. Difference between TGA and high-resolution TGA. Difference between DSC and MDSC.
7. Molecular mass determination: main experimental methods and their applications.
8. Rheology of polymers: main definitions. Discussion of the rheological curves.
9. Mechanical and dynamic mechanical properties: main definitions and description of stress-strain curves.
1. General definitions and introductory concepts on polymer science.
2. Mechanisms of polymer synthesis: families of polymerizable monomers; chain growth steps; chain transfer reactions; conversion dependence of the molecular masses in the various polymerization processes.
3. Discussion of the stereo-control in polymerizations with coordination mechanism.
4. Definitions and characteristics of the solid state of polymers.
5. Knowledge of the main values of the glass transition and melting temperatures of the commercial polymers mentioned during the course.
6. Thermo-analytical methods: main experimental methods and their applications. Difference between TGA and high-resolution TGA. Difference between DSC and MDSC.
7. Molecular mass determination: main experimental methods and their applications.
8. Rheology of polymers: main definitions. Discussion of the rheological curves.
9. Mechanical and dynamic mechanical properties: main definitions and description of stress-strain curves.
CHIM/04 - CHIMICA INDUSTRIALE - CFU: 6
Lezioni: 48 ore
Docente:
Ranucci Elisabetta
Turni:
Turno
Docente:
Ranucci ElisabettaSiti didattici
Docente/i
Ricevimento:
Ricevimento con orario libero, preferibile appuntamento via e-mail
Studio piano 3° Dipartimento di Chimica