1、Polymer Synthesis and Modification TechnologyCourse SyllabusCourse Code：09040003Course Category：Major SelectiveMajors：Intensive Training Class Semester：SpringTotal Hours：36 HoursCredit：2Lecture Hours：36 HoursLab Hours：0Practice Hours：0Textbooks：Contemporary Polymer Chemistry, H. R. Allcock, F. W. La
2、mpe, J. E. Mark, Chemical Industry Press 2006, ISBN: 7502576444.References：1) Polymer Science and Technology, J. R. Fried, Chemical Industry Press 2005, ISBN: 7502568255.2) Principles of Polymer Chemistry, A. Ravve, Chemical Industry Press 2008, ISBN: 9787122009845.3) New techniques of polymer synth
3、esis (the second edition), editor: Jianguo Wang, Chemical Industry Press 2004, ISBN: 7502553150.4) Polymer modification, editors: Yaguang Qi and Xuming Xue, Chemical Industry Press 2005 ，ISBN: 7502563237/G.1618.5) Synthetic technique of polymers, Deren Zhao, Weisheng Zhang, Chemical Industry Press 2
4、004, ISBN: 7502516816.6) Engineering plastics by blending modification, Rusheng Deng, Chemical Industry Press 2005， ISBN: 750254416x.7) Polymer modification, Guoquan Wang, Xiufeng Wang, China Light Industry Press 2008, ISBN: 9787501963621.8) Principles and applications of polymer blending modificati
5、on, Guoquan Wang, China Light Industry Press 2007, ISBN: 9787501957415.9) PMMA resins and their applications, Zhanbiao Ma, Chemical Industry Press 2002, ISBN: 7502533885.Teaching Aim：Polymer synthesis and modification technology is a major selective course in College of Chemistry, Chemical Engineeri
6、ng and Materials Science at the Soochow University. It can be also regarded as a special and basic course for students in different specialties. By taking this course, the students can master the basic concepts, theories and methods of polymer synthesis and processing and will understand the charact
7、eristics of different kinds of polymers.Polymer chemistry is aimed at synthesis and reaction of polymers, and polymermodification underlies wide use of polymeric materials, so both of them are very important to each other. This course will be focused on a) basic theory of polymer reactions, b) relat
8、ionships among reaction theory, structures, properties and applications, and c) basic technology of polymer modification preparation. The students are expected to master the following contents after attending this course:1) to understand some basic concepts such as polymerization rate, average degre
9、e of polymerization, macromolecular microstructure and copolymer composition and some important reagents such as monomer, initiator, catalyst, chain transfer agent, inhibitor, emulsifier and dispersant; 2) to learn basic polymerization methods such as normal and“living”/controlled free radical polym
10、erization, step-growth polymerization, and ionic polymerization; 3) to learn classification of topological polymers including dendrimers and their self-assembly; 4) to master basic theory and methods of polymer modification, molding and production.After taking this course, the students will learn ho
11、w to synthesize polymers from the raw materials, can under the different characteristics of various polymeric materials and can handle the modification process of common polymers. The students can also be capable to solve theengineering problems and can make up the gap between the theoretical knowle
12、dge of polymer chemistry and practical production.To study the present course, the students had better possess the basic knowledge of differential courses, such as polymer structure and properties, polymer chemistry, polymer physics and materials science and engineering. The students should also hav
13、e the basic understandings of mechanics and engineering. The course will be very useful for their further studies and future employment.Chapter OneFree radical polymerization Hours：two weeks，4 hours in totalContents1-1 Chain polymerization familyClassified by the nature of reactive center: radical p
14、olymerization, cationic polymerization, anionic polymerization, coordinating ionic polymerization.Chain polymerization consists of a sequence of three steps: Initiation reaction, Propagation reaction, Termination reaction.Examples on polymers prepared via free radical polymerization.1-2 Mechanism of
15、 radical polymerizationGenerationoffreeradicals:thermaldecomposition,photochemicaldecomposition, oxidation-reduction (redox) reaction, high energy particle radiation.The activity of a free radical is determined by its structure.Reactions of the free radical: addition reaction, coupling reaction, dis
16、proportionation reaction, dissociation reaction, and transfer reaction.1-3 Monomer structure and types of polymerizationMost of the mono olefin, conjugated diolefin, alkyne and carbonyl compounds, and some of the heterocyclic compounds can be polymerized from the thermodynamic viewpoint.However, the
17、 selectivity of various monomers to different polymerization mechanisms varies greatly and depends on some factors such as the electronic effect of the substituents involving the inductive or resonance effect and steric effect.1-4 Elementary reactions of the radical polymerizationThey normally refer
18、 to chain initiation, chain propagation, and chain termination. Perhaps the polymerization is accompanied by chain transfer reaction and so on.1-5 Characteristics of the radical polymerizationThe rate of initiation is the lowest one, which controls the overall rate of polymerization.In conclusion, t
19、he characteristics of radical polymerization are slow initiation, fast propagation, fast termination, and easy transfer.1-5 Initiators and initiationTypes of initiators: azo initiator, organic peroxide initiator, inorganic peroxide initiator, redox initiation system.Kinetics of initiator decompositi
20、on: initiator decomposition rate, initiator efficiency, and choice of initiator.Other initiation systems: thermal-initiated polymerization, light initiated polymerization, and high energy radiation initiated polymerization.1-6 Rate of radical polymerizationPolymerization rate and measuring method, s
21、teady-state polymerization rate equation, effect of temperature on polymerization rate, rate constants of elementary reaction and main parameter, autoacceleration, types of rate changing during the polymerization process, inhibition and retardation.1-7 Molecular weight and chain transfer reactionMol
22、ecular weight is an important parameter to characterize polymers.Factors affect the rate of polymerization, such as the concentration of initiators, the concentration of monomers, the polymerization temperature, and so on, which also affect the molecular weight. Chain transfer reac tion usually does
23、nt affect the rate of the polymerization, however, affects the molecular weight very much.Molecular weight is also an important part in kinetics study. Kinetic chain length and the degree of polymerization.Problems:1 What are molecular weight and polydispersity of polymers?2 Please list the repeatin
24、g unit of the following polymers and monomers to synthesize them: PSt, PMMA, PAA, PVA, PIP, PTFE.3 Please list the resources to generate free radicals. 4 Please list main reactions of radicals.5 Please list three monomers which can be polymerized via radical, ionic and coordination polymerizations.6
25、 Can 1,1-diphenylethylene be subjected to polymerization? Why?7 Please draw chemical structures of poly(styrene-alt-maleic anhydride). 8 Please list elemental reactions of chain polymerization.9 Please list the types of microstructures for monosubstituted vinyl monomers.10 Please list the types of c
26、hain transfer reaction in free radical polymerization and give two examples of chain transfer agents.11 What are the characteristics of radical polymerization?12 Notions: efficiency of initiation, kinetic chain length, autoacceleration (gel effect), radical life, polymerization rate, inhibition, ret
27、ardation13 Chemical structures: AIBN, BPO, KPS, cumyl hydroperoxide14 Please list the relationship between degree of polymerization and kinetic chain length. 15 Please explain basic principles of dilatometer method.Chapter Two“Living”/controlled radical polymerizationHours：two weeks，4 hours in total
28、Contents2-1 Living and controlled systemsLiving systems: constant number of polymer chains, no permanent chain stopping reactions,ndormant and active state, control of chain-growth, narrow MWD (Poisson), M vs. monomerconversion is linear.Controlled systems: side reactions do occur, however still hav
29、e a control over end groups, topology, monomer sequence.2-2 Living polymerizationLiving polymerization is a form of addition polymerization where the ability of a growing polymer chain to terminate has been removed.Chain termination and chain transfer reactions are absent, and the rate of chain init
30、iation is much larger than the rate of chain propagation.The result is that the polymer chains grow at a more constant rate than seen in traditional chain polymerization and their lengths remain very similar.Living polymerization is a popular method for synthesizing block copolymers since the polyme
31、r can be synthesized in stages, each stage containing a different monomer.Additional advantages are predetermined molecular weight and control over end groups.2-3 Types of living polymerizations Living anionic / cationic polymerization Ring-opening methathesis polymerization“Living”/controlled free
32、radical polymerizationGroup transfer polymerization Living Ziegler-Natta polymerization2-4 How to realize a living system?Reversible activation, chain transfer processes, and combination of both. Ionic polymerization:Easy design of polymeric architectures: Very selective reactions, requires extreme
33、reaction conditions such as low temperatures and high purity solvents and reagents, expensive to undertake for industry (catalysts cost, various requirements).Free radical polymerization: Good tolerance towards impurities, wide range of (functionalized) monomers, widely employed in industry via bulk
34、, solution, emulsion/suspension polymerization, inhibition by oxygen, and lack of selective reactions.2-5 Iniferter method Developed by Otsu in 1982Thermal-initiated iniferter:Mostofthembelongtoderivatives of1,2-disubstituted tetraphenylethanesPhoto-initiated iniferter: Compounds comprising diethyld
35、ithiocarbamate2-6 Catalytic chain transfer polymerization (CCTP)Certain low-spin cobalt complexes, typical Mon/Co ratio of ca. 1062-7 Nitroxide mediated living radical polymerizationTypical nitrooxy radical is 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO)High temperature is required (110 oC), and the
36、re are limited number of monomers2-8 Transition metal mediated living radical polymerization (Atom transfer radical polymerization, ATRP)ATRP process using CuBr/bpy catalytic systemApplication of ATRP: To prepare well-defined macromolecules with predetermined MW and loww/nnpolydispersity (1.04 M M 1
37、.50, 300 M 200,000), to control macromolecular architecture,to control microstructure of macromolecules, and to prepare macromonomers and functionalized polymers with COOH, OH, NR1R2 and vinyl groups.2-9 Reversible addition-fragmentation chain transfer (RAFT) polymerization Control over MW & archite
38、ctureWide range of monomers Ambient reaction conditions One-step processSimple purification of productRAFT agents: only a few agents are available commercially (expensive!) Thio-chemistry: hazardous and smellyApplication of RAFT processProblems:1 What are basic features of living polymerization syst
39、ems?2 Please list the main types of “living”/controlled radical polymerization. 3 Please list the basic mechanism and application of ATRP.4 Please list the basic mechanism and application of RAFT polymerization, and describe the primary roles of Z and R groups of RAFT agent.Chapter ThreeIonic polyme
40、rization Hours：two weeks，4 hours in totalContents3-1 OverviewSome monomers, like alkenes and substances with rings, can undertake ionic chain polymerization with an ionic initiator.According to the sorts of the active center at the end of long chain, ionic polymerization can be classified into three
41、 categories: cationic, anionic and coordination.The active center of cationic polymerization is a carbocation, and the active center of cationic polymerization is a carbocation.3-2 Cationic Polymerization Initiator and monomerAlkenes with electron-donating substituents are cationic polymerizableA ca
42、tionic catalyst or initiator could react with the above-mentioned monomer to produce a carbocationic active center.The cationic initiators can be classified into two categories: strong proton acid and Lewis acid. Cationic polymerization mechanism: Cationic polymerization belongs to chain polymerizat
43、ion, and it contains initiation, propagation, transfer, and termination.The feature of the cationic polymerization is fast initiation, rapid propagation, very extremely easy transfer and comparatively hard to termination, in which a terminator is often indispensable.Reaction kinetics3-3 Polymerizati
44、on Initiator and monomerTypical anionic polymerizable monomers: styrene, MMA and acrylic nitrile etc.All types of monomers are p-p conjugated system or that with electron attracting group, making the density of electron cloud of double bond declineThe anionic active center reacts with double bond by
45、 addition reactionMechanism: The anionic polymerization still belongs to the chain polymerization. It consists of 3 elementary reactions: initiation, propagation, and termination.Living polymer:As long as no termination occurs, though all monomers are used up, the polymer still remains activity. Whe
46、n new monomer is added, the polymerization restarts. When another kind of monomer is added, a block copolymer produces.Many initiators can be used in the living polymerization. The most convenient is metal Na and naphthalene natrium initiator.Alkali metal Na transfers the electron of the outer layer
47、 to the monomer, to form a monomer anion radical, which is produced, through the radical double-group termination, double anion to take on the living polymerization.Reaction kineticsApplication: To synthesize monodisperse polymers, to measure the anionic polymerization rate constant, to prepare bloc
48、k copolymers, and to prepare telechelic polymers.3-4 Comparison between radical & ionic polymerizations Monomer and initiatorMechanism Kinetics TemperatureEffect of solvent and other chemicalsProblems:1 Take Na-naphthalene based anionic polymerization of styrene for example, please describe the basic mechanism and application of living anionic polymerization. How about the relationship between polymerization degree and kinetic chain length?2 Please describe the main applications of living anionic polymerizat
