CHAPTER POLYMER CHEMISTRY Introduction: Functionality Degree of Polymerization. Classification of Polymers — Natural and Synthetic, Thermoplastic and Thermosetting — Types and Mechanism of Polymerization: Addition (Free Radical, Cationic, Anionic and Living); Condensation and Copolymerization—Properties of Polymers: Tg, Tacticity, Molecular Weight — ~ Weight Average, Number Average and Polydispersity Index — Techniques of | Polymerization: Bulk, Emulsion, Solution and Suspension — ~ Structure, Properties and Uses of; PE, PVC, PC, PTFE, PP, Nylon | 6, Nylon 66, Bakelite, Epoxy; Conducting Polymers — ~ Polyaniline and Polypyrrole. : 1.1 INTRODUCTION Polymers are extremely large molecules that are essential ® our very existence. They are the main constituents of our food (starch, protein, etc.) our clothes (polyester, nylons, etc.) our houses (wood cellulose, alkyd paints, etc.) and our bodies (poly nucleic acids, proteins, etc.). The term polymer is not new for human beings, in fact, it was present four billion years ago, since the formation of earth was over. The origin of life occurred by a polymer named protein. Protein is a complex molecule formed by the combination of elements like Carbon, Hydrogen, Oxygen and Nitrogen, which were present on the earth’s surface. Almost the whole human Sody is built around the same polymer. Polymers are the chief products of modern chemical idustry which form the backbone of the present society. They Save become compounds of light weight, high strength, flexible, chemical resistant with special electrical properties. 144:12 Engineering Chemistry 1.1.1 Monomer A Monomer is a small molecule (micromolecule), which combines with each other to form a macromolecule called the polymer. ooo 4 & Monomers (Many small molecules) Fig. 1.1(a) Representation of Monomers 1.1.2 Polymers Polymers are macromolecules (large molecule) formed by the repeated linking of large number of small molecules called monomers. The word polymer is derived from two greek words, “poly” means many and “mers” means part or numbers. monomer Polymers (One large molecule) Fig. 1.1(b) Representation of Polymers Example 1: Polyethylene is a polymer formed by the repeated linking of large number of Ethylene molecules. nCH, = CH, ———> -.-- CH, - CH, — CH,- CH, — --- Ethylene Polyethylene (Monomer) (Polymer)Poly’ mer Chemistry 1.3 >> ye Example 2 : PVC isa polymer formed by the repeated linking of large number of Vinyl Chloride molecule. nCH,=CH ——>-~ -CH,- CH - CH- CH- ~~ | | | cl cl cl Vinyl chloride Polyvinyl chloride (Monomer) (Polymer) 1.1. Some Important Monomers and their Corresponding Polymers are listed as follows: — — CH, - CH, - Ethylene Polyethylene (PE) CH,=CH—-CH=CH, | -CH,-CH=CH-CH,- Butadiene Polybutadiene CH, CH, Propylene Polypropylene (PP) ~ CH, -CH- Polystyrene (PS) —CH,- CH- | | a cl Polyvinyl Chloride (PVC)<< 14 CH, = CH | CN Acrylonitrile Engineering Chemistry —CH,- CH - | CN Polyacrylonitrile (PAN) CH,= CH | COOH Acrylic acid - CH, -CH- | COOH Polyacrylic acid (PAA) CH, = CH | COOCH, Methyl Acrylate ~CH, ~CH- | coocH, Polymethyl Acrylate (PMA) CH, =C-CH=CH, | CH Isoprene 3 —CH,-C=CH_-CH< | CH, Polyisoprene CH, =C-CH=CH, | cl Chloroprene =CH,-C=CH-—CH, - | cl Polychloroprene1.2 FUNCTIONALITY The number of functional groups present in a monomer is called functionality of a monomer. Depending on the functionality of the monomers we can prepare: 1. Linear 2. Branched 3. 3D cross — linked polymersCi, = CH, (Ethylene) CH, - COOH | CH~- COOH | CH, - COOH Ticarballylic acid Two bonding sites are due to presence of one double bond. Two functional groups are present. Three functional groups are present. aa Bifunctional monomer. Bifunctional monomer, Trifunctional monomer. Three functional groups are present. Trifunctional monomer. (Methyl alcohol) Only one reactive site is present. They cannot undergo polymeriation. Mono- functional monomer. (Chain Terminator)44 1.6 Engineering Chemistry 1.2.1 Significance (a) Bifunctional Monomers In the case of a bifunctional monomer, two reactive groups are attached side by side to each other to form a linear or straight’ chain polymer. Each monomeric unit in the linear chain is linked by primary covalent bonds, but different chains are held together by secondary Vanderwaal’s forces of molecular attraction. This gives the possibility of chain movement in one direction. ~ ‘Secondary Vanderwaal's forces of molecular attraction * . Chain formation by Bifunctional monomers Covalent bonds ar Fig. 1.2(a) Linear Chain Polymer from a Bifunctional Monomer Mixture of two different bifunctional monomers will form linear chain copolymers. Secondary Vanderwaal's forces of molecular attaction ? 3 os] gle Mixture of Bifunctional Chain formation by —¥ monomers Covalent bonds Fig. 1.2(6) Linear Chain Copolymer from a Bifunctional MonomerTrifunctional Monomers In the case of trifunctional groups, monomer molecules connected to each other by covalent bonds, resulting in the ion of three dimensional networks as shown in fig. 1.3. ers of higher functionality also produce networks). When a trifunctional monomer gets mixed with a small of bifunctional monomer, they form branched chain as shown in fig. 1.4. The movement of polymer chain, in a branched polymer, restricted than that in a straight chain polymer. m mA Side chain A > a a ‘Trifunctional monomers Main chain Fig. 1.3. 3D - Network Polymer Fig. 1.4. Branched Chain Polymer from a Trifunctional Monomer Polyfunctional Monomers In case of polyfunctional groups, monomer molecules connected to each other by covalent bonds, resulting in the ion of a three dimensional network as shown in fig. 1.5.441.8 Engineering Chemistry The movement of polymer chain is completely restricted by strong cross-links. +++ Fy ++4+—. oe Polyfunctional monomers Poyfunctional ‘monomer unit 30 - network polymers Fig. 1.5. 3D — Network Polymer1.3 POLYMERISATION Polymerisation is a process in which large number of monomers combine to give a polymer with or without elimination of small molecules like H,O, NH,, etc. Example 1: Polymerisation of Ethylene nCH, = CH, ———> -€ CH, ~ CH, ~ CH, — CH, - CH, +; Ethylene Polyethylene (Monomer) (Polymer) Example 2: Polymerisation of Butadiene nCH, = CH - CH, = CH,—-> CH, =CH =CH= CH, > n-Butadiene Polybutadiene (Synthetic rubber) 1.3.1 Degree of Polymerisation (DP) The number of repeating units (n) in a Polymer chain is known as the degree of polymerisation. There may be hundreds or thousands of monomer molecules linked together in a polymer molecule. It is calculated from the following relation.7 Chemistry 1.9 >> Degree of i Molecular weight of the polymer polymerisation (n) Molecular weight of the repeating unit Example : 3CH, = CH, ——> - CH, - CH, ~ CH, - CH, - CH, In this example, totally 3 repeating units are present in the Polymer chain. Therefore, the degree of polymerisation is 3. Diigomers Polymers with low degree of polymerisation are known = Oligomers. The molecular weight of Oligomer ranges from 580-5000 amu. High Polymers Polymers with high degree of polymerisation are known high polymers. The molecular weight of high polymers range Som 10,000 to 2,00,000 amu. PROBLEM 1: Calculate the degree of polymerisation for (i) A low density Polyethylene with a molecular weight of 20,000 amu. “®) A high density Polyethylene with a molecular weight of 3.90.000 amu. Formula used: Degree of Polymerisation (DP,,) _ { Molecular weight of Polyethylene — Ma Molecular weight of Ethylene My<< 1.10 Engineering Chemistry Reaction : n(CH, = CH,) ——> -C CH, — CH, 5; Ethylene Polyethylene Molecular weight of Ethylene (C,H,) = 28.05 amu (i) Degree of Polymerisation Dp = Molecular weight of low density Polyethylene e Molecular weight of Ethylene _ 20,000 amu 28.05 amu ~. The Degree of Polymerisation DP, = 713. (ii) Degree of Polymerisation Dp = Molecular weight of high density Polyethylene ie Molecular weight of Ethylene _ 300,000 amu 28.05 amu DP, = 10,695 “. The Degree of Polymerisation DP, = 10,695.