Polymer Science
A.Y. 2025/2026
Learning objectives
This course aims to provide students with a clear and in-depth understanding of the fundamental concepts relating to the synthesis and physical-chemical characterization of polymers, thus preparing them to study advanced courses in the discipline. In the initial phase, basic polymer concepts and definitions will be introduced. Subsequently, students will delve into both classical and advanced mechanisms of polymer synthesis, with particular attention to the controlled synthesis of complex polymer architectures, including controlled radical polymerization and ring-opening polymerization. The course will also cover the physical chemistry of polymer solutions and blends, the thermal properties of polymers and the techniques for their determination. Finally, a complete overview of the different methods of determining molecular masses, both traditional and advanced, will be provided.
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, using living polymerization mechanisms.
4. Define the basic concepts related to polymer solutions.
5. 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.
6. Interpret simple calorimetric traces of the DSC type, identifying melting and glass transition temperatures and physical aging phenomena.
7. Interpret simple thermogravimetric (TGA) plots to determine the thermal stability of polymers and the composition of polymer blends.
8. Interpret simple MALDI-TOF spectra for the identification of the distribution of the molecular masses of the polymers and their structural details.
9. Interpret simple SEC spectra and determine the molecular weights 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, using living polymerization mechanisms.
4. Define the basic concepts related to polymer solutions.
5. 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.
6. Interpret simple calorimetric traces of the DSC type, identifying melting and glass transition temperatures and physical aging phenomena.
7. Interpret simple thermogravimetric (TGA) plots to determine the thermal stability of polymers and the composition of polymer blends.
8. Interpret simple MALDI-TOF spectra for the identification of the distribution of the molecular masses of the polymers and their structural details.
9. Interpret simple SEC spectra and determine the molecular weights of polymers.
Lesson period: First semester
Assessment methods: Esame
Assessment result: voto verbalizzato in trentesimi
Single course
This course cannot be attended as a single course. Please check our list of single courses to find the ones available for enrolment.
Course syllabus and organization
Single session
Responsible
Lesson period
First semester
Course syllabus
1. Introduction to polymer science
Plastic materials and their relevance. Definition of monomer, macromolecule and repeating unit. Natural, synthetic, artificial, and inorganic polymers. Statistical, alternating, block and graft copolymers. Geometric isomerism, configurations and conformations of polymers. Molecular masses of polymers and their distributions; numerical and weight average values.
2. Step-by-step polymerization mechanism
Polymerizable monomers. Dependence of the polymerization degree on the reaction parameters; number and weight distribution functions of molecular masses. Synthesis of cross-linked polymers.
3. Free radical polymerization mechanism (FRP)
Polymerizable monomers. Main reaction steps: initiation, propagation, termination, and chain transfer. Dependence of the average polymerization degree on the reaction parameters. Inhibition and delay reactions; self-acceleration. Depolymerization reaction and "ceiling temperature".
4. Polymerization with ionic mechanism
Polymerizable monomers and mechanism-specific initiators (cationic and anionic); dependence of the polymerization rate on the solvent nature. Cationic mechanism: chain transfer. Anionic mechanism: living polymerization.
5. Stereospecific polymerization
Polymerizable monomers. Ziegler/Natta type catalysts: composition, structure and general reactivity. Iso- and syndiospecific catalysts. Supported catalysts and use of the third and fourth components. Chain termination and transfer steps. Metallocene-type catalysts: composition, structure and general reactivity. Role of methylaluminoxanes. Iso- and syndiospecific catalysts. Effect of symmetry on catalyst specificity.
6. Controlled radical polymerization mechanisms (CRP): nitroxide mediated polymerization (NMP); atom transfer polymerization (ATP); reversible addition-fragmentation chain transfer (RAFT) polymerization.
7. Ring opening polymerization: polymerizable monomers. Classification of the initiators: electrophilic and nucleophile ring opening. Pseudo-ionc polymerization. Polymers of industrial interest.
8. Group transfer polymerization: polymerizable monomers and chain growth mechanisms.
9. Copolymerization reactions. Definition of reactivity ratios and their determination methods.
10. Physical chemistry of polymer solutions and polymer blends.
11. Self-assembly of polymers, polymeric micelles and polymersomes.
12. Molecular weight analysis: solution viscometric; osmometry; light scattering; size exclusion chromatography; MALDI-TOF analysis.
13. Amorphous and crystalline state: requirements for achieving crystallinity; morphology of polymer crystals; crystallization rate. Amorphous polymers and glass transition temperature.
14. Thermal analysis. Scanning calorimetry (DSC): operating principle; analysis of glass transition and melting temperatures. Dependence of the shape of the thermograms on the heating and/or cooling rate. Annealing and physical aging. Thermogravimetric analysis: operating principle and application to the study of the thermal and thermo-oxidative decomposition of polymers.
Plastic materials and their relevance. Definition of monomer, macromolecule and repeating unit. Natural, synthetic, artificial, and inorganic polymers. Statistical, alternating, block and graft copolymers. Geometric isomerism, configurations and conformations of polymers. Molecular masses of polymers and their distributions; numerical and weight average values.
2. Step-by-step polymerization mechanism
Polymerizable monomers. Dependence of the polymerization degree on the reaction parameters; number and weight distribution functions of molecular masses. Synthesis of cross-linked polymers.
3. Free radical polymerization mechanism (FRP)
Polymerizable monomers. Main reaction steps: initiation, propagation, termination, and chain transfer. Dependence of the average polymerization degree on the reaction parameters. Inhibition and delay reactions; self-acceleration. Depolymerization reaction and "ceiling temperature".
4. Polymerization with ionic mechanism
Polymerizable monomers and mechanism-specific initiators (cationic and anionic); dependence of the polymerization rate on the solvent nature. Cationic mechanism: chain transfer. Anionic mechanism: living polymerization.
5. Stereospecific polymerization
Polymerizable monomers. Ziegler/Natta type catalysts: composition, structure and general reactivity. Iso- and syndiospecific catalysts. Supported catalysts and use of the third and fourth components. Chain termination and transfer steps. Metallocene-type catalysts: composition, structure and general reactivity. Role of methylaluminoxanes. Iso- and syndiospecific catalysts. Effect of symmetry on catalyst specificity.
6. Controlled radical polymerization mechanisms (CRP): nitroxide mediated polymerization (NMP); atom transfer polymerization (ATP); reversible addition-fragmentation chain transfer (RAFT) polymerization.
7. Ring opening polymerization: polymerizable monomers. Classification of the initiators: electrophilic and nucleophile ring opening. Pseudo-ionc polymerization. Polymers of industrial interest.
8. Group transfer polymerization: polymerizable monomers and chain growth mechanisms.
9. Copolymerization reactions. Definition of reactivity ratios and their determination methods.
10. Physical chemistry of polymer solutions and polymer blends.
11. Self-assembly of polymers, polymeric micelles and polymersomes.
12. Molecular weight analysis: solution viscometric; osmometry; light scattering; size exclusion chromatography; MALDI-TOF analysis.
13. Amorphous and crystalline state: requirements for achieving crystallinity; morphology of polymer crystals; crystallization rate. Amorphous polymers and glass transition temperature.
14. Thermal analysis. Scanning calorimetry (DSC): operating principle; analysis of glass transition and melting temperatures. Dependence of the shape of the thermograms on the heating and/or cooling rate. Annealing and physical aging. Thermogravimetric analysis: operating principle and application to the study of the thermal and thermo-oxidative decomposition of polymers.
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
Frontal lessons with the help of slides.
Teaching Resources
1. Instructor notes available on the course site on the Ariel platform
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, classifying the families of polymerizable monomers, the chain transfer reactions, the control of molecular weights in the various polymerization processes.
3. Control of stereochemistry in polymerizations with coordinated mechanisms. Dependence of stereochemical control on the symmetry of metallocene catalysts.
4. Definitions and characteristics of polymer solutions and blends.
5. Definitions and characteristics of the solid state of polymers.
6. Knowledge of the main values of the glass transition and melting temperatures of the commercial polymers mentioned during the course.
7. Thermal analysis methods: main experimental methods and their applications. Difference between TGA and high resolution TGA. Difference between DSC and MDSC.
8. Methods for determining molecular masses: main experimental methods and their applications.
1. General definitions and introductory concepts on polymer chemistry.
2. Synthesis mechanisms of polymers, classifying the families of polymerizable monomers, the chain transfer reactions, the control of molecular weights in the various polymerization processes.
3. Control of stereochemistry in polymerizations with coordinated mechanisms. Dependence of stereochemical control on the symmetry of metallocene catalysts.
4. Definitions and characteristics of polymer solutions and blends.
5. Definitions and characteristics of the solid state of polymers.
6. Knowledge of the main values of the glass transition and melting temperatures of the commercial polymers mentioned during the course.
7. Thermal analysis methods: main experimental methods and their applications. Difference between TGA and high resolution TGA. Difference between DSC and MDSC.
8. Methods for determining molecular masses: main experimental methods and their applications.
CHIM/04 - INDUSTRIAL CHEMISTRY - University credits: 6
Lessons: 48 hours
Professor:
Ranucci Elisabetta
Professor(s)
Reception:
Free time, preferable appointment by e-mail
Office 3rd floor Department of Chemistry