Advanced Chemistry and Physics of Polymers
A.Y. 2023/2024
Learning objectives
The course is intended for students who have attended fundamental courses in chemistry or industrial chemistry and who plan to acquire advanced knowledge on modern techniques of synthesis and characterization of polymers. The course is preparatory to monographic or specialized courses in polymer science and technology.
Expected learning outcomes
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.
Lesson period: Second semester
Assessment methods: Esame
Assessment result: voto verbalizzato in trentesimi
Single course
This course can be attended as a single course.
Course syllabus and organization
Single session
Responsible
Lesson period
Second semester
Course syllabus
1. Introduction to polymer science
General definitions and classifications of polymers. Plastics and their relevance. Natural, synthetic and artificial, inorganic polymers. Statistical, alternating, block and graft copolymers and their relevance. Geometric isomerism, configurations and conformations of polymers. Molecular weight of polymers: molecular weight 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 in the presence of monofunctional monomers; time dependence of the polymerization degree; number and weight distribution functions of molecular weights. 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 chain-growth or step-wise mechanism. Living polymerization.
8. Group transfer polymerization
9. Molecular weight analysis: 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 ttransition emperature, 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/or 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 and artificial, inorganic polymers. Statistical, alternating, block and graft copolymers and their relevance. Geometric isomerism, configurations and conformations of polymers. Molecular weight of polymers: molecular weight 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 in the presence of monofunctional monomers; time dependence of the polymerization degree; number and weight distribution functions of molecular weights. 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 chain-growth or step-wise mechanism. Living polymerization.
8. Group transfer polymerization
9. Molecular weight analysis: 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 ttransition emperature, 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/or 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.
Prerequisites for admission
Basic knowledge of organic chemistry included in the Organic Chemistry I course of the 1st level degree course (bachelor degree). These include nomenclature, structure and general reactivity of aliphatic and aromatic compounds; reactivity of alkenes, alkynes, aliphatic halides, carboxylic acids; synthesis of esters, amides, urethanes, urea.
Teaching methods
Lectures with the aid of slides.
Teaching Resources
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.
Assessment methods and Criteria
The exam will consist of a written test in which the student is 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 in both theoretical and laboratory sections. The score will vary from 18 to 30 proportionally to the correctness of the answers.
1. General definitions and introductory concepts on polymer chemistry.
2. Synthesis mechanisms of polymers, with reference to the families of polymerizable monomers, the chain transfer reactions, and to the trend and control of molecular weights in the various polymerization processes.
3. Control of stereochemistry in polymerizations with coordination mechanism. Dependence of stereochemical control on the symmetry of metallocene catalysts.
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. Thermal analysis methods: main experimental methods and their applications. Difference between TGA and high resolution TGA. Difference between DSC and MDSC.
7. Methods for determining molecular weights: 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 chemistry.
2. Synthesis mechanisms of polymers, with reference to the families of polymerizable monomers, the chain transfer reactions, and to the trend and control of molecular weights in the various polymerization processes.
3. Control of stereochemistry in polymerizations with coordination mechanism. Dependence of stereochemical control on the symmetry of metallocene catalysts.
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. Thermal analysis methods: main experimental methods and their applications. Difference between TGA and high resolution TGA. Difference between DSC and MDSC.
7. Methods for determining molecular weights: 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 - INDUSTRIAL CHEMISTRY - University credits: 6
Lessons: 48 hours
Professor:
Ranucci Elisabetta
Educational website(s)
Professor(s)
Reception:
Free time, preferable appointment by e-mail
Office 3rd floor Department of Chemistry