Chemistry of Macromolecules   (1055H)

Academic year:

2012/2013.

Attendance requirements:

1201A + 1202A

ECTS:

8

Study level:

Study program:

Teacher:

Vesna V. Antić

Assistant:

Marija V. Pergal, M.Sc.
junior research assistant, Institute of Chemistry, Technology and Metallurgy, Njegoševa 12, Beograd

Hours of instruction:

Weekly: four hours of lectures + four hours of labwork (4+0+4)

Goals:

1. Familiarizing students with important aspects of modern chemistry of macromolecules, the molecular structure of macromolecules, the ways of performing synthesis, as well as the properties and application of the most important industrial polymers.
2. Acquiring fundamental knowledge of mechanism and kinetics of chain and stepgrowth polymerizations, as well as the ways of regulating molecular weights and molecular weight distribution of polymer.
3. Mastering basic techniques of performing chain and stepgrowth polymerizations.
4. Overviewing of the properties and application of polymer materials as function of their molecular structure.

Outcome:

—

Teaching methods:

Lectures, laboratory practice and homeworks.

Extracurricular activities:

—

Coursebooks:

Main coursebooks:

• S. M. Jovanović, J. Đonlagić, Hemija makromolekula, TMF, Beograd, 2004. (ISBN-86-7401-181-0).
• J. Đonlagić, Hemija makromolekula - praktikum, TMF, Beograd, 1999. (ISBN-86-7401-117-9).

Supplementary coursebooks:

• G. Odian, Principles of Polymerization, 4^th ed., Wiley, New York, 2004.
• H. G. Elias, An Introduction To Polymer Science, 1^st ed., VCH, Weinheim, 1997.

Additional material:

—

Lectures:

5 points (4 hours a week)

Syllabus:

1. Introduction - Basic concepts, definitions and nomenclature. Classification of polymers. Structure of polymers – constitution, i.e. chemical composition, size and size distribution of macromolecules, conformation or shape of single macromolecule, organization of macromolecules or polymer assemblies. Dependence of macromolecular macroscopic properties on molecular structure.
2. Stepgrowth polymerization - polycondensation and polyaddition. Mechanism and kinetics of stepgrowth polymerization. Reactivity of functional groups. Equilibrium in polycondensation reactions. Linear molecular size of polycondensation products. Molecular weight distribution in linear polycondensation products. Dendrimers and hyperbranched polymers. Theories of gel formation. Overview of the ways of synthesis, properties and application of some industrially significant polycondensation polymers.
3. Polymerization as chain reaction. Influence of monomer molecular structure on the way of initiating polymerization. Thermodynamical and kinetic aspect of chain polymerization. Critical temperatures and temperature range within which reactions can be carried out.
4. Radical polymerization. Mechanism and kinetics of elemental reactions of polymerization. Kinetics of polymerization under ideal conditions. Self-acceleration of polymerization. Inhibitors and retardants of polymerization. Kinetic chain length and average degree of polymerization. Temperature and pressure influence on polymerization rate and degree of polymerization. Molecular weight and molecular weight distribution of polymers.
5. Cationic polymerizations, their monomers, active centers (carbenium and oxonium ions), initiators and initiation reactions, propagation reactions, termination and transfer reactions. Kinetic expressions for the rate of cationic polymerization reactions.
6. Anionic polymerizations - monomers and initiators. Polymerizations in protic solvents, kinetic scheme and molecular weight distribution of polymer. Anionic polymerization in aprotic solvents, polymerization kinetics and molecular weight distribution of "living" polymers. Role of ionic pairs and solvent influence on polymer structure.
7. Stereospecific polymerization, initiated by heterogeneous and homogeneous catalysts of Ziegler-Natta-type. Metallocene catalysts. Mechanism of stereospecific polymerization.
8. Copolymerization reactions. Instantaneous copolymer composition equation and reactivity coefficient of macroradicals. Different types of copolymers, copolymerization parameters and change of copolymer composition with conversion. Determination of monomer reactivity coefficient.
9. Techniques of polymerization reactions by free radicals: polymerizations in bulk, emulsion, suspension, solution, as well as precipitation polymerizations.

Labwork:

10 points (4 hours a week)

Syllabus:

It is intended for every student to perform eight syntheses, and the choice is among following:

• Synthesis of aromatic polyesters and aliphatic polyamides by interfacial polycondensation.
• Synthesis of alkyd resin.
• Synthesis of unsaturated polyester.
• Synthesis of telechelic dihydroxyl terminated poly(ethylene adipate) and its crosslinking by toluene diisocyanate.
• Preparation of flexible and rigid polyurethane foams.
• Polymerization of methyl-methacrylate in bulk.
• Polymerization of styrene in emulsion.
• Polymerization of methyl-methacrylate in suspension.
• Precipitation polymerization of acrylonitrile.
• Synthesis of poly(oxymethylene) by ring-opening polymerization of trioxane.
• Synthesis of poly(dimethylsiloxane) by a heterogeneous catalyzed equilibrium polymerization.

Colloquia:

15 points

Written exam:

20 points

Oral exam:

50 points