Advanced Chemistry and Physics of Polymers

A.Y. 2019/2020
6
Max ECTS
48
Overall hours
SSD
CHIM/04
Language
English
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
The course will provide knowledge on the controlled synthesis of complex macromolecular structures, the structural characterization of polymers, the physico-chemical properties (including solution properties) and physical properties (including thermal and rheological properties of polymers). Students will become skilled of structure-property relationships for polymers.
Course syllabus and organization

Unique edition

Responsible
Course syllabus
1. Introduction to polymer science: general definitions and classifications of polymers. Plastics and their relevance. Natural, synthetic, artificial and 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. Radical polymerization mechanism: polymerizable monomers. General process features: rapid, exothermic reactions; main reaction steps: initiation, propagation and termination, chain transfer. Dependence of the average polymerization degree on the reaction parameters. Chain transfer: Mark-Houwink-Sukurada equation. Inhibition and delay 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: polymerizable monomers. Composition and structure of Ziegler/Natta catalysts and their general reactivity. Polymerization mechanism through poly-insertion: monometallic and bimetallic mechanism. Ziegler/Natta iso- and syndiospecific catalysts. Supported catalysts. Catalysts of higher generations: use of the third component. Kinetics of polymerization. Termination and chain transfer steps. Metallocenes: Composition and structure of metallocene catalysts. Role of methylaluminum oxanes (MAO). Polymerization through poly-insertion mechanism. Stereospecific control: iso- and syndiospecific catalysts. Effect of the catalyst symmetry on stereospecificity.
6. Controlled radical polymerization mechanisms (CRP): nitroxide mediated polymerization (NMP); ATP (atom transfer polymerization); reversible addition-fragmentation transfer (RAFT) polymerization . Control of molecular mass and structural details (terminals, block sequence etc).
7.Ring opening polymerization: polymerizable monomers. Classification of the initiators: electrophilic and nucleophile ring opening. Polymerization kinetics. Polymers of industrial interest.
8. Group transfer polymerization: polymerizable monomers. Classification of initiators and catalysts. Associative and dissociative mechanisms. Merits and pitfall of GTP.
9. Biobased polymers: definition of biopolymer and bioplastics. Artificial biopolymers. Biobased polymers production routes. Biopolymers market potential in Europe.
10. Characterization of polymers: application of FT-IR and NMR spectroscopies to the structural characterization of polymers.
11. Molecular weight analysis: solution properties of polymers. Solution viscosity. Size exclusion chromatography off line and online light scattering. MALDI-TOF mass analysis.
12. Thermal properties 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 temperature temperature, Tg, as a non-thermodynamic transition. Crystallization rate.
13 Differenital Scanning Calorimetry (DSC): classification of existing instruments and operating principle. Analysis of glass transition temperature and melting temperature. Examples of DSC thermograms. Dependency of the shape of the thermograms from the rate of heating and / or cooling. Annealing and physical aging.
14. Introduction to the thermogravimetric analysis (TGA) of polymers: operating principle and application to the study of thermal and thermo-oxidative decomposition of polymers.
14. Rheology of polymers: general definitions and concept of viscoelasticity. Flow curves and flow regimes. Dependence of viscosity on temperature, time, molecular weight, deformation rate, shear stress.
Prerequisites for admission
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 physical characterization of polymers. The course is preparatory to monographic or specialized courses in polymer science and technology. Prerequisites: basic knowledge of organic and physical chemistry.
Teaching methods
Lecturing. Attendance is recommended.
Bibliography
1) Textbook on polymer chemistry: Principles of polymerization, George Odian, Wiley.
2) Instructor notes on all topics covered.
Course home page: https://eranuccipc.ariel.ctu.unimi.it.
Assessement methods and criteria
Assessment method: final written test with open questions. No intermediate tests are planned. Students will be asked to answer general questions regarding all the topics covered in the course.
Test duration: 2-2.5 hours depending on text length.
Score will vary in the range 18 to 30 out of 30 and will be proportional to the number of correct answers.
The test results will be communicated by e-mail a few days after the exam and registration will be conditioned on acceptance by te student.
CHIM/04 - INDUSTRIAL CHEMISTRY - University credits: 6
Lessons: 48 hours
Professor: Ranucci Elisabetta