Polymer Chemistry

Goals The course is intended for students who have followed fundamental courses in chemistry or industrial chemistry, 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.


Acquired skills
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. Structure-property relationships will be emphasized.


Course content
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. 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 metallocence catalysts. Polymerization through poly-insertion mechanism. Stereospecific control.
6. Controlled radical polymerization mechanisms.
7. Ring opening polymerization: polymerizable monomers. Classification of the initiators: electrophilic and nucleophile opening of the ring.
8. Group transfer polymerization.
9. Biobased polymers.
10. Poymer characterization: FT-IR and NMR analysis of polymers.
11. Molecular weight analysis: solution properties of polymers. Solution viscosity. Size exclusion chromatography light scattering off line and online. MALDI-TOF mass analysis.
12. 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 temperature temperature, Tg, as a non-thermodynamic transition. Crystallization rate. Scanning calorimetric analysis (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.
13. Thermogravimetric analysis: 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.


Suggested prerequisites: basic knowledge of organic chemistry and physical chemistry.


Reference material: George Odian: Principles of polymerization, Wiley. Instructor notes.



Assessment method
Written test with open questions. Students will be required to answer general questions concerning all subjects treated in the course. The evaluation will be proportional to the number of correct answers.

Language of instruction
English

Attendance Policy:
Attendance is not obligatory but preferred.


Mode of teaching:

Class lessons


Website:
https://eranuccipc.ariel.ctu.unimi.it/v5/home/Default.aspx