Supporting material for students registered to subject: Macromolecular chemistry S112003 Teacher: Jan Merna, Department of Polymers, Institute of Chemical Technology,Prague Lecture authored by Jan Merna is licensed under a Creative Commons Attribution- NonCommercial-NoDerivs 3.0 Unported License Sources: Prokopová I.: Makromolekulární chemie, VŠCT Praha, 2007. (educational text in Czech) Merna J.: Polymers Instantly, educational text in English, freely accessible from http://merna.eu/teaching/macromolecular-chemistry/ Encyclopedia of Polymer Science and Technology, J.Wiley Sons, Interscience, Publ., New York, 1964-1991
merna@vscht.cz, B130 MACROMOLECULAR CEMISTRY Lectures + exercises (2+1) Recommended literature: Stevens M.P.: Polymer Chemistry An Introduction. Oxford University Press, Inc., New York 1999. Chanda M.: Introduction to Polymer Science and Chemistry. A Problem Solving Approach. CRC Press Boca Raton 2006. Young R.J., Lovell P.A.: Introduction to Polymers. Third Edition. CRC Press Boca Raton 2011. Supporting materials: http://merna.eu/teaching/macromolecular-chemistry/ Evaluation: written tests: One test in the mid of semester Final exam test
Outline of the course: 1. Basic terms, history, nomenclature 2. Structure of macromolecules, molecular weight. 3. Molecular structure and properties of polymers. 4. Polymerizability of low molecular substances. 5. Free radical polymerization - elemental reactions. 6. Kinetics of free radical polymerization. 7. Free radical copolymerization. 8. Ionic polymerization and copolymerization. 9. Insertion polymerization, polymerization practice. 10.Ring-opening polymerization. 11.Step-growth polymerization - characterization, reactivity of monomer functional groups. 12.Polycondensation - mechanism and kinetics, molecular weight distributions. 13.Polyadditions - typical syntheses. 14.Reactions of polymers.
ISTORY OF MACROMOLECULAR CEMISTRY 1820 processing of natural rubber 1839 rubber vulcanization 1862 celluloid- nitrocellulose+camphor 1897 Galalith - casein (milk protein) and formaldehyde (1838) polyvinylidenchloride? (1839) polystyrene
ISTORY OF MACROMOLECULAR CEMISTRY 1906 Bakelite phenol-formaldehyde resin 1915 methyl-rubber - poly(dimethylbutadiene) 1926 1939 alkyd resins, aminoplastics, polymethylmethacrylate, polybutadiene, polyvinylacetate, polystyrene, polyvinylchloride, polyethyleneoxide, polychloroprene, unsaturated polyesters, polyizobutylene, butadiene-styrene rubber, polyamide 66 1939 1945 polyvinylidenchloride, PE (LD), polyamid 6, polyurethanes, polyakrylonitrile, silicons 1946 1955 epoxides, polytetrafluorethylene, polyethylenterephtalate, polycarbonates, PE (D) 1956 1965 polybutadiene (cis-1,4), polypropylene, polyformaldehyde, aromatic polyamides, block copolymers Sty-Bu-Sty
Fathers of macromolecular chemistry ermann Staudinger (1881-1965), NP 1953 Wallace Carothers (1896-1937) Paul J. Flory (1910-1985), NP 1974 theory of polycondensation solution and solid phase polymer properties, theory of crosslinking Karl Ziegler Giulio Natta, NP 1963
Year 2010 2000 eeger & MacDiarmid & Shirakawa 1990 1980 1970 1960 Natta & Ziegler 1950 0 2 4 6 8 Nobel prices in polymer science
Polymer production worldwide 300 Mt/year (7% of oil) 1. PE 80 Mt/y 2. PP 50 Mt/y 3. PET 50 Mt/y 4. PVC 30 Mt/y 5. PS-styrene polymers Age of plastics Rubbers- 20 Mt/y Price of basic polymers 1-2 /kg
Polymers advantages and role in today s society: Low density Cheap manufacture and sources Easy processing Insulation properties-thermal+electro Polymers save more energy than used for their production (buildings, transportation) Food protection Fabrics-synthetic fibres-save land, fertilizers, water
Utilization of plastics in Europe:
Price + performance Production volume (t/y) Plastics classification: Consumable (commodity)_pe,pp,ps, PVC, PET Engineering (construction) plastics-better properties Special (high-performance) Thermoplastics classification Special Engineering Commo dity
Plastics recycling in Europe
Basic terms polymer ( macromolecular compound) Oligomer monomer polymerization polyreaction step-growth chain-growth ring-opening regular (irregular) polymer constitutional unit Constitutional repeating unit (CRU) Monomeric unit (mer) Polymerization degree Copolymer
Basic terms C polyreaction C C C A monomer A A A Regular polymer C C C A A A Irregular polymer,,,... C C2 C A A constitutional unit C2 C C A A Repeating constitutional units (CRU), n monomer (ethylene) Polyethylene with degree of polymerization n Monomeric unit CRU
Polymer nomenclature IUPAC. Pure Appl. Chem. 84, 2167 2169 (2012).
Polymer nomenclature PRINCIPALS OF STRUCTURE BASED POLYMER NOMENCLATURE Choice of preferred CRU Naming of CRU (according to nomenclature rules of org. chem.) prefix poly- The order of subunit seniority in preferred CRU: 1. heterocycles 2. heteroatoms 3. C-cycles 4. C-chains Naming of pref. CRU: listing of names of largest possible subunits CRU usually divalent C atom with double bond have the lowest locant number free valences in C-cycles lowest locant numbers
ierarchy of heterocyles More unsaturated (less hydrogenated) unit is favoured ierarchy of heteroatoms O,S, Se, Te, N, P, As, Sb, Bi, Si, Ge, Sn,. N C N C N N poly(4,2-pyridindiylimino-1,4-phenylene-benzylidene) ierarchy of C-cycles 1. Subunit with largest amount of cycles 1. podjednotka s největším počtem kruhů >
2. Subunit 2. podjednotka with the largest s největším individual individ. ring kruhem > 3. podjednotka s největším počtem atomů společných dvěma cyklům 3. Subunit with the highest number of common atoms between two cycles > 4. Subunit 4. podjednotka with the lowest s nejnižšími number of čísly locants lokantů in first v prvním different rozdílném point of cycles bodě connection spojení kruhů 5. The most 5. podjednotka unsaturated nejméně cycles is hydrogenovaná the most preferred 8a 8 7 6 9 10 1 2 5 4 3 5a > > > 8 7 6 8a 1 2 9 3 4 10 5 10a
Substituents a) Included to trivial name of subunit b) Named using prefixes joined to the name of corresponding subunit Cl 2 1 3 6 4 5 C Br n poly[(6-chlorocyklohex-1-ene-1,3-diyl)(1-bromoethylene)] poly[(6-chlorocyklohex-1-ene-1,3-diyl)(1-bromoethanediyl)]
Functional derivatives as a part of CRU as substituents ad b) poly[oxy(2-methoxycarbonyl)ethane-1,1-diyl]
2. STRUCTURE OF POLYMERS - chemical constitution - type and arrangement of structural units - molar mass configuration conformation - physical mutual arrangement of macromolecules
1. Constitution Monomer with functionality two : linear polymers (a) Monomer with functionality two or higher : branched (b) crosslinked polymers (c) (a) (b) (c)
Types of enchainment of monomer units C C C Connection head to tail RC R R R C R C R C R Connection tail to tail Resp. head to head
Modes of monomer units connection for conjugated diene polymerization symmetrical diene: butadiene C C 1,4 - addition C C C C 1,2 - addition (the same as 3,4-addition) Non-symetrical substituted diene: isoprene 4 1 1,4-addition n 1 2 3 4 1 2 1,2-addition 2-methylbuta-1,3-diene isoprene 3 4 3,4-addition
Special macromolecular architectures comb Grafted-copolymer star ladder polycatenane dendrimer cyklic polyrotaxane
Copolymers: statistical alternating block grafted
2. Macromolecules configuration Reasons for spatial isomers: a) tetrahedral arrangement of substituents on asymmetrical carbon atom zig-zag conformation of polyethylene
Reasons for spatial isomers : b) Planar arrangement of substituents on carbon atoms connected by double bond cis isomers trans isomers
Polymer tacticity - arrangement (sequence) of stereoisomeric centers isotactic polymer syndiotactic polymer Atactic polymer R R R R R R
Ditactic polymers erythro-diizotactic threo-diizotactic erythro-disyndiotactic threo-disyndiotactic
Ditactic polymers R,,,, R R R R R R R erythro-diizotactic R, R, R, R, R R R R threo-diizotactic R R,,,,, R R R R R R R R,,, R R R R R R erythro-disyndiotactic threo-disyndiotactic
3. Molecule conformation Ethane sp synperiplanar (sp) conformation ap antiperiplanar (ap) conformation Potential energy -180 sp -120 ap -60 sp 0 ap 60 sp 120 ap 180 sp Angle of rotation
Molecule conformation Butane! least probable!
Rotational movement of atoms in polymer chain 5 1 3 2 4 Free rotation is restricted by steric barriers and by interaction with neighbor macromolecules
Chain segment rotating part of chain (between nodes) ideal chain (freely-jointed chain) Dimensions of macromolecular coil r max Average end-to-end distance r = 0 o r opt o
Molar mass of polymers Polymer: mixture of polymerhomologues nonuniform polymer n 1, n 2,...n i number of molecules M 1, M 2,...M i molar mass of molecules Types of average molar mass of polymers - number M n n M i n i i x M i i - mass (weight) M w n M i n M i 2 i i w M i i - viscosity 1 a M a Mv wi i - z-average M z n M i n M i 3 i 2 i w M i w M i 2 i i
Uniform polymer: all macromolecules are of the same size Relationships between molar mass averages: Non-uniform polymer M n < < M w M z Uniform polymer M n M w M z
Analogy of polymer molar mass 498 pcs à 1 kg = 498 kg 2 pcs à 250 kg = 500 kg 500 pcs 998 kg 400 pcs à 1 kg = 400 kg 100 pcs à 6 kg = 600 kg 500 pcs 1000 kg Mn M w (498 x 1 2 x 250) kg 1,996 kg 498 2 2 2 (498 x 1 2 x 250 ) kg 125,75 kg 498 x 1 2 x 250 Mn M w (400 x 1 100 x 6) kg 2,00 kg 400 100 2 2 (400 x 1 100 x 6 ) kg 4,00 kg 400 x 1 100 x 6
Amount of polymer Distribution of polymer molar mass -the relationship between the number of moles of each polymer species (n i ) and the molar mass (M i ) of that species Mn Mw M z x i Mol. mass 0 Mol. mass
Methods of molar mass determination M n : osmometry, ebulioscopy, cryoscopy, determination of end-groups M w : light scattering M v : viscometry Determination of molar mass distribution: Size exclusion chromatography-sec (gel permeation chromatography-gpc) PS calibration x absolute detection
Separation mechanism of SEC