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.1.4 CLASSIFICATION OF POLYMERS Polymers are classified into four main categories as shown in fig. 1.6. They are as follows: 1. Based on the Source. (Origin) 2. Based on the Structure.1.11 >> 3. Based on the Mode of Synthesis. 4. Based on the Intermolecular Forces. Based on the Source (Origin) On the basis of source or origin, the polymers are ssified into two types. They are: (a) Natural Polymers. (b) Synthetic Polymers. Natural Polymers Synthetic Polymers Linear Polymers Branched Chain Polymers Cross linked Polymers Addition Polymers Condensation Polymers Elastomers Fibers Thermoplastics Thermosetting polymers Fig. 1.6. Classification of Polymers _ Natural Polymers The polymers which are isolated from natural ials such as plants and animals are called natural44 1.12 Engineering Chemistry Few examples of natural polymers are listed below. @ Starch’ It is a polymer of a-D-Glucose. It is a chief food reserve of plants. : (ii) Cellulose It is a polymer of £-D-Glucose. It is a chief structural material of the plants. NOTE: Starch and Cellulose are very common examples of Polysacchari photosynthesis. a (iii) Proteins These are polymers of a-amino acids. These are the building blocks of animal cells. They have generally 20 to 100 a-amino acids, joined together in a highly organized arrangement. (iv) Nucleic Acids These are the polymers of various nucleotides. RNA (Ribo Nucleic Acid) and DNA (Deoxyribo Nucleic Acid) are the examples. (v) Natural Rubber Substance obtained from latex is known as natural rubber. It is a polymer of unsaturated hydrocarbon, 2-methyl-1, 3-butadiene (Isoprene). nCH, = C - CH = CH, ———» — CH, - C= CH-CH, - | | CH, CH, Isoprene Polyisoprene (Natural rubber)Synthetic Polymers The polymers which are prepared artificially in the ies are referred to as synthetic polymers (or) man-made Examples : Polyethylene, Teflon, Nylon, Orlon, Bakelite, PVC. , Terylene, Polystyrene, etc. Based on the Structure Based on the structure, the polymers are classified as (a) Linear Polymers. (6) Branched chain Polymers. (c) Cross-linked Polymers. Linear Polymers in linear polymers, the monomeric units are linked together mm a long straight chain. cample : Polyethylene, Polyester, Nylon, etc. Branched Chain Polymers These are the polymers, where the monomeric units are ed to constitute long chains (main chain). Example: Glycogen and Amylopectin. Cross-linked Polymers In Cross-linked polymers, the monomeric units are linked by only covalent bonds to constitute a three dimensional They are also called as Network Polymers.441.14 Engineering Chemistry Example : Bakelite, Melamine, Formaldehyde resin, etc. (a) Linear polymers @ Jong chain branched chain (b) Branched chain polymers main chain * cross linked (c) Cross-linked poly) Fig. 1.7. Classification based on Structure 1.4.3 Based on Synthesis Based on the mode of synthesis, the polymers are classified into two types. They are: (a) Addition Polymers. (b) Condensation Polymers. (a) Addition Polymers When the monomeric units are repeatedly added to form long chains, without the elimination of any by-product molecules. The product formed are called addition polymer. Examples : : (i) Polyethylene is produced from Ethylene nCH, = CH, ——> -€ CH, —CH, >, Ethylene Polyethylene or PolyetheneChemistry 1.15 >> PVC is produced from Vinyl Chloride nCH, = CH———> -( CH, — CH), | | cl cl Vinyl chloride Polyvinyl chloride ‘Condensation Polymers When the monomer units are repeatedly added to form with the elimination of simple molecules like 4,0, /H, etc. The products formed are called condensation Example 1 : sHOOC € CH,);COOH + nH,N-¢ CH,),NH, Adipic acid | Hexamethylene diamine H H | | +C-£CH, },C—N-CH, gN 4,1 2nH,0 | ll oO oO Nylon - 6,6. + %n HCHO Saget Formaldehyde OH OH OH OH or orer ogre Bakelite44 1.16 Engineering Chemistry 1.4.4 Based on Intermolecular Forces On the basis of the magnitude of intermolecular forces like Vanderwaal’s forces and Hydrogen bonds, the polymers are classified into four types. They are: (a) Elastomers. (b) Fibers. (c) Thermoplastic Polymers. (d) Thermosetting Polymers. (a) Elastomers These are the polymers which have weak intermolecular forces. Example: Rubber (Natural / Synthetic) (b) Fibers These are the polymers which have strong intermolecular forces such as Hydrogen bonds. These are thread-like polymers. Example: Silk, Terylene, Nylon, etc. i oO " ea eee a aces i | 0 H i { <— Hydrogen Bonding Oo iF Hydrogen Bonding in Nylon - 6,6.‘Thermoplastics These are the polymers in which various chains are held by weak Vanderwaal’s forces of attraction. The intermolecular forces of attraction of these polymers stween elastomers and fibers. There is no cross-linking sen the polymer chains. Example: Polyethylene, Polystyrene, PVC, etc. ermosetting Polymers These are the polymers in which the various chains are gether by strong covalent bonds (or) cross links. Example: Bakelite 1.3. Differences between Thermoplastic and Thermosetting ] These are formed condensation polymerisation. All the polymer chains are linked by strong covalent | bonds. These consist of three dimensional network structure. _ All the polymer chains i ee wectter by weak _ These consist of long _ chain linear polymers.Engineering Chemistry oO inecring Chemistry 4. | These soften on heating These do not soften on and harden on cooling. heating. On prolong heating they burn. 5. | These are weak, soft and | These are strong, hard and less brittle. more brittle. 6. | These can be softened, These cannot be reshaped reshaped and reused. and reused. 7. | These are soluble in These are insoluble in organic solvents. organic solvents. 8. | These can be reclaimed These cannot be reclaimed from wastes. from wastes. 9. | These have low molecular | These have high molecular weight. weight. | 10. Eg: Polyethylene, PVC Eg: Bakelite Weak force Covalent bond or cross link Se Pott1.5 TYPES OF POLYMERISATION Polymerisation is classified into two types. They are: 1. Addition Polymerisation. 2. Condensation Polymerisation. 1.5.1 Addition (or) Chain Growth Polymerisation Addition polymerisation is a reaction that gives a product, which is an exact multiple of the original monomeric molecule. The bifunctional molecule is formed from the monomer molecule by intermolecular rearrangement.Polymer Chemistry 1.19 >> The addition polymerisation must be initiated by the @pplication of heat, light, pressure or a catalyst. There is no elimination of small molecules like H,0, NH,, HCl, ete. Example1: Polymerisation of Ethylene to produce Polyethylene. nCH, = CH, Heat/Pressure hie GU =; + Polystyrene (PS)<< 1.20 Engineering Chemistry Table 1.4. Typical Addition Polymers Ethylene Polyethylene (PE) Household CH, = CH, {CH;=CH,}, products, pipes, toys, bottles. 2. | Propylene Polypropylene (PP) | Sterilisable CH, = CH CH, - CH}, hospital | | equipments, CH, CH, water pipes. 3. | Styrene Polystyrene (PS) Cheap CH, = CH £CH, — CH}, moulded objects, foam. 4. | Acrylonitrile Polyacrylonitrile Sweaters. CH, = CH (PAN) | 4CH, — CH}, CN | CN 5. | Isoprene cis-1,4- Car tyres, CH, =C—CH=CH, | polyisoprene mechanical | +CH,-C=CH-CHL), | goods. CH, | i CH; 6. | Vinyl Chloride Polyvinyl Chloride Rain coats, CH, =CH-Cl | (PVC) | flexible : iCra CH} | pipes, toys, ata ie water pipes, cl sheathing on electrical cables.Polymer Chemistry 1.21 >> Vinyl Acetate Polyvinyl Acetate | Emulsion CH,=CH-O-C-CH, | (PVA) paints, ll +CH, — CH}, chewing oO gum. oO | oO | C= | CH, Methyl Polymethyl Aeroplane Methacrylate Methacrylate windows. (PMMA) CH. | 4CH, — C}, | c=0 3 1.5.2 Condensation (or) Step Growth Polymerisation It is defined as the reaction between simple polar groups containing monomers with the formation of polymer and elimination of small molecules like H,O, HCI, Ethanol, etc. Since the reaction occurs in steps and the polymer chain grows with each step. It is also called step-growth polymerisation and the polymers formed are called step-growth polymers.44 1.22 Engineering Chemistry Example 1: Condensation of Hexamethylene Diamine and Adipic Acid to produce Nylon — 6,6 (Polyamide). + 2nH,O nN ¢ CH,; NH, + nHOOC -¢ CH, 3; COOH fHN-€H NH C-CcH, 04 I | oO oO Nylon - 6,6 (Polyamide) Example 2: Polymerisation of Caprolactam to produce Nylon - 6. CH ch, CH. n| H | | ——> e - CH, + N CH, oH I 5 ‘o—nH o q ° Caprolactam Nylon - 6 Here, no elimination of small molecules takes place, but cyclic opening occurs. Example3: Condensation of Urea and Formaldehyde to produce Urea Formaldehyde resin. nHLN-C-NH, + nH-C-H —> {HN-C-NH-CH},+nH,O I ll oO Oo Urea I oO Formaldehyde Urea-Formaldehyde resinPolymer Chemistry 1.23 >e 1.5.3 Copolymerisation It is a joint polymerisation of two (or) more different kinds of monomer molecules. Oe OeOeOeO Different kinds of monomers | Copolymerisation Sane Copolymer molecules ©-6.0.6 Fig. 1.8. Diagrammatic Representation of Copolymerisation High molecular weight compounds obtained by copolymerisation are called copolymers or mixed polymers. Example: Copolymerisation of Styrene and Butadiene gives Styrene Putadiene rubber. n[CH, = CH — CH = CH,] + nCH, = CH: Butadiene * opolymerisation Styrene | © -€ CH, — CH = CH— CH, — CH,— CH}, Polybutadiene-co-Styrene (Styrene Butadiene rubber, GR-S rubber)< 1.24 Table 1.5. Differences between Addition and Condensation Polymerisation Engineering Chemistry The monomer must have atleast one multiple bond. Eg: Ethylene The monomer must have atleast two identical (or) different functional groups. Eg: Glycerol Monomers add on, to give a polymer without the elimination of H,O, HCl, CH,OH, etc. Monomers condense to give a polymer with the elimination of HO, HCl, CH,OH, ete. Homo chain polymer are formed. Hetero chain polymer are formed. Number of units decreases steadily throughout the reaction. Thermoplastics are produced. Eg: Polyvinyl Chloride (PVC) + Monomers disappear early. in the reaction. Thermosetting plastics are produced. Eg: Bakelite Chain grows at active centres. Stepwise intermolecular condensation takes place. Molecular weight of the polymer is an integral multiple of molecular weight of the monomer. Molecular weight of the polymer need not be an integral multiple of the monomer.Polymer Chemistry 1.25 >> 8. | High molecular mass Molecular mass of the polymer are formed at once. | polymer rises steadily throughout the reaction. 9. | Longer reaction times have | Longer reaction times are a little effect on molecular _| essential to obtain high weight, but give higher molecular weight. yields. 10. | Only monomer and polymer | All possible molecular are present during the weight molecules like course of polymerisation. dimers, trimers, tetramers and oligomers, etc., are present. 11. | Eg : Polymerisation of Eg : Condensation of Ethylene. Urea & Formaldhyde. reac EIS eon | Ee] {HN-C-NH-CH,},+nH,0 4,04, 3 Polyethylene Urea-Formaldehyde Resin 12. | Initiator (Catalyst) Most reactions have high generates active species AE and hence usually that attack monomer. The heating is required. process of polymerisation is | Uncatalysed or Catalysed called exothermic. processes are possible. Addition Polymerisation Reaction time ——» Condensation Polymerisation ! Reaction time ——»Polymer Chemistry 1.27 >> 1.7 MECHANISM OF ADDITION POLYMERISATION The mechanism of addition polymerisation is explained by the following three mechanisms. 1. Free Radical Mechanism. 2. Tonic Mechanism and 3. Co-ordination Mechanism. All the above mechanisms occur in three major steps namely, (i) Initiation. (ii) Propagation and (iii) Termination. 1.7.1 Free Radical Mechanism (i) Initiation step Initiation step is considered to involve two reactions. (a) First reaction involves production of free radicals by homolytic dissociation of an initiator (or catalyst) to yield a pair of free radicals (R’). 1 : RR Se RR Initiator (1) Free Radicals (b) Second reaction involves addition of this free radical to the first monomer to produce a chain initiating species. H H R'+ CH)= es R—-CH)—C° x x Free radical First monomer Chain initiating species44 1.28 Engineering Chemistry ren CSE. (ii) Propagation step It involves the growth of chain initiating species by successive addition of a large number of monomer molecules. H H H H | I I | R—CH,— C'+nCH,>=C—> R +CH,—C+ CH -C | | | | x x Xx x Growing chain (iii) Termination step Termination of the growing chain of the polymer occurs either by, (a) Coupling (or) Combination. (b) Disproportionation. (a) Coupling It involves coupling of free radical of one chain end to another free radical forming a large polymer molecule (macromolecule). H 4H HH Nie seas coupling Et Rew CH)— C+ "C—CH,™R- ——> RCH) — C— C— CH mR ee a Xe x x (b) Disproportionation | It involves transfer of a Hydrogen atom of one radical centre to another radical centre. This results in the formation of two polymer molecules, one saturated and another unsaturated. The final product of addition polymerisation is known as the ‘Dead Polymer’.Polymer Chemistry 1.29 >> Hew oA aH t I plsdab Disproportionation Least RewC—C + (CCR Rw C=C | od { eX x H x Unsaturated polymer + H H 14 H—C—C-~~“R hcg d xX H Saturated polymer (Dead Polymer) 1.7.2 Ionic Mechanism Depending on the nature of ions, the ionic mechanism or ionic polymerisation is divided into two categories. They are: 1. Cationic Polymerisation. 2. Anionic Polymerisation. 1. Cationic Polymerisation In this type of polymerisation, initiators (catalysts) and monomers are used during the chain growth; however, the initia~ tion is done by a proton and the propagation is carried out by a Carbonium ion (Carbocation). Here, the initiators used are strong lewis acids such as BF,, AICL,, SnCl,, TiCl, with a co-catalyst, water. The monomers are Styrene, Methyl Styrene, many Vinyl Ethers and Isobutylene. Mechanism @ Initiation step It involves the formation of the. Carbonium ion (chain imitiating species).<< 1.30 Engineering Chemistry First, the strong Lewis acid such as BF, in the presence of small amount of H,O, forms hydrate which exists as ion pairs. BE EF 70 | | F“AB4SH= of —sl7p—pB — On |-4-H® | | Carbonium ion F F Be (Cation) Catalyst Co-catalyst Counter ion (lewis acid) (Anion) (or) e © (BF,OH] -—--H Secondly, the H’ ion attacks the x electron pair of the monomer molecule and forms a Carbonium ion. CY @ [BF; onyx? CH, = CH—+>H — CH, — CH [BF; OH] = mo | i x x (or) = ° CH; — CH [BF;0H] | (anion) x Carbonium ion (ii) Propagation step @ ® oO CH; — CH [BF; OH] + CH) = CH—> CH;— CH— CH) — CH [BF; OH] | | | | x x x x (Monomer) @ CH; — CH — CH2— CH [BF3 ouf+ CH, = CH { | | x xX xX (Monomer) @ CH; — CH — CH;— CH — CH;— CH [BF; OHP. \ \ I x xX x G. \ gPolymer ChainPolymer Chemistry 1.31 >> It involves the successive addition of monomer molecules and transfer of the charge to the newly added monomer molecule. Since, the addition of monomer units are increased, the chain Keeps on growing. (iii) Termination step (a) It involves removal of the catalyst by the addition of proton to the counter ion. CH;— CH~~~CH, — Cu (BF,OHf—> CH; — CH~“~CH = CH | ! | | x x x x (Growing Polymer Chain) (Arrest Polymer Chain) + [BF,OHPH® In this process, a proton is added and BF, hydrate is re-formed. It is called “ion-pair precipitation”. (b) In this process, termination occurs by simple ‘Coupling’, when a covalent bond is formed between Carbonium ion (C®) and the counter-ion. OH Il cH,— CH cH, — On [BF,OHP—> CH — CHC — CH | 1 I I x ode x x + BE; 2 Anionic Polymerisation Anionic Polymerisation was used to produce synthetic elastomers from Butadiene at the beginning of the 20" century. thitially, alkali metals in liquid ammonia were used as initiators. But now, the initiators, used are generally the organo-alkali compounds such as Ethyl Sodium, Butyl Lithium, Phenyl Lthium, Triphenyl Methyl Potassium and alkali metal amides seach as NaNH., LiNH,.Engineering Chemi. Vinyl monomers with electron withdrawing groups more readily polymerized using anionic polymerisation. The monomer molecules are Styrene, Butadi Acrylonitrile, Methyl Methacrylate. The order of activity using an amide ion initiator is Acrylonitrile > Methyl methacrylate > Styrene > Butadiene. Mechanism (i) Initiation step It involves the formation of Carbanion (chain initiati species). The organo-alkali compounds exist as ion pairs follows: NaNH,—> NH® + Na® (Sodamide) (anion) (cation) Now, a negatively charged ion (anion) attacks z elect pair of the monomer molecule and forms a Carbanion. é ™ 8 NH, + CH=CH —>H,N— CH — CH Anion x x (Initiator) Monomer Carbanion (ii) Propagation step It involves the successive addition of monomer molec and transfer of charge to the newly added monomer molecule. Q 8 HN — CH, — CH + CH; = CH—» H,N— CH) ioe a | | ' x x x x Monomer Carbanion8 CH + CH, =CH | | x x x New Monomer — CH, — CH — CH; — | 2° HN — CH. — SH. =, Che = oH = CHy.—CH | xX xX x Carbanion (Growing Polymer Chain) Termination step Termination of the growing polymer chain occurs by Ammonia. — CH; — CH-~CH, — CH — CH, — cx +H — Neb 2 of 7 Amionia HN — CH; ~ CH~w CH — CH ~ Cli) — Ci + NH. I x x x NHS + NP —> NaNH, Polymers No formal termination happens in the last step, because product i is a stable Macroanion. Szwarz named such stable e species as “living polymers”. These macroanions have used to produce block copolymers. Termination is brought about by addition of Water, Ethanol, onia, Carbondioxide or Oxygen. Living polymers are generally characterized by, ¢ Aninitiation rate much larger than the polymerization rate. ¢ Stabilization of the living end groups allowing the formation of macromers, block copolymers and star polymers.44 1.34 Engineering Chemistry a Chem 1.7.3 Coordination Polymerization These reactions are catalysed by organo-metallic compounds. The monomer molecules used are corey Dienes and Olefines. A coordination bond is formed between a Carbon atom of the monomer and the metal atom of the catalyst and thus leading to the formation of monomer — catalyst complex. Mechanism (i) Initiation step M-R+CH,=CH —+ M-CH,-CH-R | | x x Organometallic (Monomer-Catalyst) compounds M=Metal ion (ii) Propagation step M- CH, ~CH—R+CH,=CH —> M—CH,—CH-CH,—CH-R I | | | x x xX x New Monomer MC, Ce CHR ae I | 28 x x New Monomer M—CH, ~ CH—CH, —CH—CH,—CH—R | | | xX x x Growing Polymer Chain (iii) Termination step Termination by transfer with monomer.M- CH, - CH- CH, - CH- CH, -CH-R —>M-H | | | x x x + CH, = CH - CH, -CH-CH,-CH-R | x | | x x Ziegler (1953) and Natta (1955) discovered this type erisation. Polymerisation : are less reactive. Easy to carry out the reaction. Free radical polymerisations polymerisation and therefore, it is called as Ziegler-Natta ‘Tbble 1.7. Differences between Free Radical and Ionic Ionic polymerisations are more selective. Most difficult to carry out the reaction. Depends only on the nature of the monomer. Strongly depends on the reaction medium. The nature of the solvent Thenature of the solvent has no effect. - has a large effect. 5. | The initiation reaction in The initiation reaction free radical polymerization _| in ionic polymerisation has high activation energy. _| has very low activation energy. 6. | The rate of free radical The rate of ionic polymerisation is slow. polymerisation is fast. Hee. Sensitivity is less. It is easy to obtain reproducible kinetic data. reproducible kinetic data. Sensitivity is high. It is difficult to obtain441.36 Table 1.8. Differences between Cationic and Anionic Polymerisation Engineering Chemistry The growing chain end bears a positive charge. Ann” The growing chain end bears a negative charge. a ln in Ol The cationic process con- sists of the movement of the a electron pair in a direction opposite to that of the chain growth. ‘of the m electron pair in-the The anionic process consists of the movement same direction as that of the chain growth. Polymerisation takes place with monomers having electron donating groups. Hi | | Eg: -R, -OR,-C=C-R and —~@) Polymerisation takes place with monomers having electron withdrawing groups. Eg:--C=N, GR, ll oO —C-—OH and-C-OR ll I oO 0 The initiators used to initiate the reaction are Lewis acids like BF,, AICI,, TiCl, and SnCl, with water or alcohols. The initiators used are generally the organo-alkali compounds such as Ethyl Sodium, Butyl Lithium and alkali metal amides such as NaNH,, LiNH,, KNH,.PROPERTIES OF POLYMERS 1 Glass Transition Temperature The temperature at which a polymer experiences the ition from rubbery to glassy state is termed as the glass ition temperature (T,)- Glassy state Rubbery state (Hard) (Soft) (BelowT,) T, (Above T,) Glass Transition Temperature Almost all amorphous polymers and many crystalline ers possess a temperature boundary as shown in fig. 1.9. e this temperature, the polymers remain soft, rubbery and ible. Below this temperature, they become hard, glassy and ‘Table 1.9. Glass Transition Temperature of some Polymers Polystyrene 100 Polyvinyl chloride 87 Polyester 69 Nylon 6:6 37 Polypropylene | 18 Polyethylene (High Density) -90 Polyethylene (Low Density) -11044 1.38 Engineering Chemistry Fig. 1.9. Specific Volume vs. Temperature The soft, rubbery, flexible state is called as rubbery or visco elastic state. The hard, glassy, brittle state is called as glassy state. Factors influencing ae The following factors influence the glass transition temperature as shown in fig. 1.10. Chain Flexibilty Plasticization ‘Gavan Factors Crystallinity Tee attractive forces Cross-linking Molecular Weight and branching Fig. 1.10. Factors Influencing T, (a) Chain flexibility Polymers with bulky side groups cause increased i due to steric hindrance and less chain mobility.Polymer Chemistry 1.39 >> ) Geometric factors Polymers that have symmetrical structure have lower a, than those with asymmetric structure. fe) Inter-chain attractive forces The presence of strong intermolecular bonds in a polymer chain will significantly increase ce (@ Molecular weight Increasing the molecular weight tends to increase the T,. fe) Cross-linking and branching For highly cross-linked systems, the i is very high. For highly branched systems, the T, is low. @) Crystallinity The value of T, will increase with increasing degree of crystallinity. (g) Plasticiation The process of adding plasticizers is known as plasticization. Plasticizers are usually non-polymeric, organic liquids of high boiling points. Addition of plasticizers to a polymer drastically reduces the T, of the polymer. Importance of Glass Transition Temperature T, is an important property of a polymer. It provides following information: ¢ It is used to know whether a polymer molecule is flexible or rigid and brittle. ¢ It gives an idea about the polymeric material, whether it will behave like plastic or rubber.<< 1.40 Engineering Chemistry * T, gives information about the right processing temperature. ¢ It is used to determine whether the polymer exhibits any mechanical stress. vere is used to convert polymeric materials into finished products by various processing techniques such as moulding, calendering and extrusion. 1.8.2 Tacticity The term tacticity is derived from the Greek word ‘taktikos’ meaning arrangement or order. Definition The orientation of functional groups in a polymer can take place in an orderly or disorderly manner with respect to the main chain and that is known as tacticity of the polymer. There are three types of Stereo-regular polymers. They are: (a) Isotactic (b) Syndiotactic (c) Atactic (a) Isotactic Polymer If all the functional groups are arranged on the same side of the main chain, the polymer is called Isotactic polymer. cl cl cl cl ci lnc atl a eaePolymer Chemistry 1.41 >> oem eer A (b) Syndiotactic Polymer If the functional groups are arranged alternatively above and below with respect to the main chain, the polymer is called Syndiotactic polymer. cl cl ci Arman cl cl (c) Atactic Polymer If the functional groups are arranged in a random manner, the polymer is called Atactic polymer. cl cl cl Sn aot sa Te 8 cl cl Table 1.10. Comparison between Isotactic, Syndiotatic and Atactic Polymer Arrangement | Same side Alternatively of the main above and chain. below with respect to main chain. Crystalline Amorphous<< 1.42 Engineering Chemistry 1.9 MOLECULAR MASS (WEIGHT) OF A POLYMER ¢ Polymers are the mixtures of molecules of different or single length chains. Polymers consisting of chains of differing lengths are called polydisperse while polymers containing only one chain length are called monodisperse. ¢ Generally, the larger the polymer, the higher is its molecular weight. Example : CH, = CH, Polymerisation. + CH,—CH,+ Ethylene Polyethylene (Monomer) (Polymer) Here, Molecular weight of Ethylene is 28. The Polyethylene molecules contain molecules of different molecular masses. -- CH, — CH, (Molecular weight 5600) tio --CH,—CH,, (Molecular weight 8400) Theo +- CH. —— CH, (Molecular weight 11200) Significance of Molecular Mass of a Polymer The knowledge of molecular weight of a polymer is very important because: ¢ Various properties of polymers such as viscosity, tensile strength, softening temperature, impact strength and heat resistance are directly dependent on the molecular weight of the polymer.er Chemistry 1.43 >> * Viscosity increases more steeply at very high molecular weight. ¢ Tensile and impact strength increases with molecular weight. * Low molecular weight polymers are soft and gum- like resins. ¢ The high molecular weight polymers are tougher and more heat-resistant. of Molecular Mass of a Polymer There are three main types of Molecular mass of polymers ly, 1. Number - Average Molecular Mass (Mn) 2. Weight -— Average Molecular Mass (Mw) 3. Viscosity — Average Molecular Mass (Mv) 1.9.1 Number — Average Molecular Mass (Ma) Definition (Ms) is defined as the total mass (w) of all the molecules @ polymer sample, divided by the total number of molecules present. Formulae Mathematically it is defined as where, N. = Number of polymer molecules. M,= Molecular mass of a polymer molecule.44 1.44 Engineering Chemistry Determination Mn is determined by measurement of colligative properties such as, (a) Lowering of vapour pressure. (b) Depression of freezing point. (Cryoscopy) (c) Elevation of boiling point. (Ebulliometry) (d) Osmotic pressure. Significance @ Mn is a good index of physical properties such as impact and tensile strengths. (ii) Mn is nota good index of other properties such as flow. 1.9.2 Weight — Average Molecular Mass (Mw) Definition My is defined as the total sum of the product of the weight and molecular mass of the monomer in a polymer divided by the total mass of all the monomer molecules. Formulae (Mathematical Expression) Mathematically, Mw is defined as | LMM; iy | ma Weight of the polymer where, w, M, i Molecular mass of the polymerIf N, denotes the number of molecules having a mass ( then, 4, = NM, Hence, the above equation may be written as Determination Mw is determined by the following techniques. They are: (a) Light — Scattering. (b) Ultra — Centrifugation. Significance / Properties + The Mw is always greater than the Mn. 1.9.3 Viscosity — Average Molecular Mass (My) My is defined by, : Wa ad y N; Me My =) == =N,M; where, a = Constant. (its value ranging from 0.5 to 0.9) N, = Number of polymers. M, = Molecular mass of the polymers. Determination My is determined from viscosity measurement.44 1.46 Engineering Chemistry Se eC Properties @ My is aways lesser than Mw (ii), My = Mw, when a = unity 1.9.4 Index of Polydispersity / Polydispersity Index Definition The ratio of the “weight — average molecular weight” to that of “number — average molecular weight” is known as Polydispersity Index (PDI). PDI= weight — average molecular weight = Mw number — average molecular weight My por =» n M4, Weight fraction W,—> Molecular mass, (m)————p> Fig. 1.11. Graphical Representation of Mn, Mw and My From the above graph, we can conclude the following: ¢ The weight — average molecular mass is greater than the number — average molecular mass. Myw>MnSince, Mw = Mn in case of monodisperse system (all molecules have identical molecular mass), the ratio = or 1 may be used as a measure of the “molecular- mass distribution” or “index of polydispersity”. The high-molecular weight fractions will have a greater effect on Mw 7 The low-molecular weight fractions will have a greater effect on Mn. Hence, Mw =Mn The viscosity — average molecular mass is lesser than the weight — average molecular mass. [My My>Mn Monodispersed System Polydispersed System (Same size molecules) (Different size molecules) PROBLEM Calculate the number-average and weight-average molecular masses of a Polyethylene polymer with the following composition.441.48 Engineering Chemistry --CH, —CH, +, is 25% + CH, — CH, is 35% + CH, —CH,+,, is 40% [Given that atomic mass of C= 12 and H= 1] Solution Mol. mass (M,) (= 28n) 11200 | 22400 No. of molecules in 100 (N,) (i) Number-average molecular mass Me 2N;M,; _ NM, +N2Mz+N3M3 XN; N,+N2+N3 _ (25x11200) + (35x 22400) + (40x 16800) 25+35+40 _ 280000+784000+ 672000 100 Mn =17360) (ii) Weight-average molecular mass = _=NM? _ NM? +N)My?+NjMz “ENM; iM, +NyMz+NMy_ 25(11200)” +35 (22400) +40(16800)? 25 (11200) +35 (22400) +40(16800) _ 16181700000 1736000 1.9.5 Measurement of Molecular Masses The molecular mass of a polymer can be measured by the Ssllowing methods, They are: 1. End group analysis. Viscometry. Light scattering method. Osmometry. Ultracentrifugation method. ye YD© TECHNIQUES OF POLYMERISATION Polymerisation process is basically classified into two They are: (a) Homogeneous (b) Heterogeneous Homogeneous Polymerisation Heterogeneous Polymerisation Polymerisation Solution Polymerisation Suspension Polymerisation Emulsion Polymerisation Fig. 1.12. Techniques of Polymerisation4 1.50 Engineering Chemistry (a) Homogeneous Polymerisation All the reactants, initiators and solvents are mutually soluble and compatible with the resulting polymer. (b) Heterogeneous Polymerisation The reactants, initiators, solvents and the polymer product are mutually insoluble. 1.10.1 Bulk Polymerisation Bulk Polymerisation as shown in fig. J.13 is carried out by adding a soluble initiator to pure monomer in liquid state. The reaction is initiated by heating or exposure to radiation. As the polymerisation proceeds, the mixture becomes | more viscous. The reaction is exothermic and the polymers are produced. (Liquid) | Fig. 1.13. Diagrammatic Representation of Bulk Polymerisation Bulk Polymerisation is carried out in the absence of any solvent or dispersant. Thus, it is the simplest method of polymerisation. Criteria Initiator and polymer must be able to dissolve in monomer. Examples : Polystyrene, PVC, Poly Methyl Methacrylate.Polymer Chemistry 1.51 >> Meee Advantages i; 5 The system is simple and requires thermal insulation. 2. The polymers obtained are highly pure. a. 4. Molecular weight distribution can be easily changed by The polymer obtained has a high optical clarity. using chain transfer agents. Un-reacted monomer can be removed by evaporation. Disadvantages Polymerisation is highly exothermic. Heat transfer and mixing become difficult as the viscosity of reaction mass increases. Very low molecular weight is obtained. Applications 1. It is used for fabrication of polystyrene pellet from styrene monomer. It is used for the production of organic glass of Poly (Methyl Methacrylate). It is used to get PVC resin from Vinyl Chloride. Low molecular weight polymers are used as plasticizers and lubricant additives. 1.10.2 Emulsion Polymerisation The water insoluble monomer is dispersed in a large amount of water and then emulsified by the addition of the surfactants. The surfactants can be anionic, cationic or non-ionic. The surfactants save the purpose of lowering the surface tension at the monomer-water interface and help to form emulsion. The excess quantity of the surfactant forms molecular aggregates known as ‘micelles’.41.52 Engineering Chemistry i Initiator + H2O Suspension t + Emulsifier Polymer in micelle y Polymer In Latex Form Fig. 1.14. Diagrammatic Representation of Emulsion Polymerisation The emulsifier molecules are made of two parts: (i) Along non-polar hydrocarbon chain. (ii) A polar group like - COONa, — SO,Na. In micelle formation, the emulsifier molecules aggregate in such a way that the polar end align themselves outward and non-polar ends come close to each other at the interior. Then the initiator (water soluble) is added and agitated at constant temperature. The surface layer of the micelle is highly hydrophilic and hence the added initiators are found at the surface. At the same time, the interior of the micelle is filled with the solubilised monomer. Therefore, polymerisation starts at the surface layer of the micelle and proceeds inwards. The monomer present in the aqueous phase enters the micelle and forms polymer. Therefore, polymerisation starts at the surface layer o! the micelle and proceeds inwards. The monomer present in the aqueous phase enters the micelle and forms the polymer as shown in fig. 1.15.Polymer Chemistry 1.53 >> Aqueous Phase P Surfactant Molecule itiator Molecule Fig. 1.15. Emulsion Polymerisation Then the polymer chains agglomerate into the fine particles and get surrounded and then stabilised by the emulsifier layer of the micelle. At the end of the polymerisation, we have fine particles of the polymer, stabilised by the emulsifier layer and dispersed uniformly in the aqueous phase. This milky white dispersion is often called ‘/atex’. The polymer can be isolated from the latex. by destabilising the emulsion.441.54 Engineering Chemistry Advantages 1. Heat is controlled by the continuous water phase. 2. Since the polymerisation occurs at the micelles, the viscosity of the medium remains close to that of water. 3. High molecular weight polymers can be made. 4. The rate of polymerisation is fast. Disadvantages 1. Surfactants remaining in the polymer are difficult to remove. 2. For isolated polymers, water removal is an energy intensive process. 3. Cannot be used for condensation and Ziegler-Natta Polymerisation. Applications 1. It is the most widely used industrial technique and monomers such as Vinyl Chloride, Butadiene, Chloroprene are polymerised by this technique 2. Polymers produced by this technique can be divided into 3 categories. They are: (a) Syntheticrubber eg. : Acrylic rubber (b) Plastics eg. : Polyvinyl Fluoride (c) Dispersions eg. : Polyvinyl Acetate, Latex Acrylic paint.Polymer Chemistry 1.55 >> peer terete OS 1.10.3 Solution Polymerisation In solution polymerisation, the monomer is dissolved in a suitable inert solvent. The chain transfer agents are added to control chain size or molecular weight. The initiator is also dissolved in the solvent medium. The whole mixture is kept under constant stirring and the polymers are produced. Solution polymerisation as shown in fig. 1.16 may involve a simple process in which a monomer, initiator, chain transfer agent and solvent are stirred together to form a solution that reacts without the need of heating or cooling. Examples: Polyacrylonitrile, Polyacrylic acid, etc. + CChain Transfer Agent (dissolved in- (dissolved in - inert solvent ) _ inert solvent ) Fig, 1.16. Diagrammatic Representation of Solution Polymerisation — Table 1.11. Types of Solution Polymerisation Monomer and solvent Soluble | Soluble Soluble | Soluble Initiator Soluble | Insoluble | Insoluble | Soluble Polymer Soluble | Soluble Insoluble | Insoluble44 1.56 Engineering Chemistry Advantages 1. Heat released by the reaction is controlled by the solvent. 2. Viscosity is negligible. 3. Auto acceleration effect is less. 4. The mixture can be stirred easily. Disadvantages 1. The removal of the solvent is difficult. 2. Solvent may cause chain transfer. 3. Rate of the reaction and the degree of polymerisation decreases on reducing the monomer concentration. 4. The isolation of the polymer from the solvent is very difficult. 5. It is difficult to get high molecular weight polymer. Applications 1. It is used in the production of Sodium Polyacrylate, a super absorbent polymer used in disposable diapers. 2. It is used to produce the polymers such as Polyacrylonitrile (PAN) and Polyacrylic acid (PAA). 1.10.4 Suspension Polymerisation Only water insoluble monomers can be polymerised by this technique. The water insoluble monomer is suspended in water, in the form of fine droplets and the initiator is added. The initiators are monomer soluble. The fine droplets are stabilised and prevented from coagulation by using suspending agents. The whole mixture is heated at a constant temperature with vigorous agitation. Polymerisation proceeds to 100% conversion and the product is obtained as spherical beads or pearls. This method is also known as bead polymerisation or pearl polymerisation as shown in fig. 1.17.Polymer Chemistry 1.57 >> Examples : Polyvinyl acetate, Polystyrene, Styrene-divinyl Benzene, etc. Monomer +Initiator 2 ' Polymerisation in suspended beads 7 + Suspending agent Stirred } Eg. Gelatin of Polymers Fig. 1.17. Diagrammatic Representation of Suspension Polymerisation Advantages 1, Easy heat removal and control. 2. Efficient viscosity control. 3. _ Isolation of the polymer is very easy. 4. High purity. 5. Product homogeneity. Disadvantages 1. Low reactor productivity. 2. This technique is applicable only for water insoluble monomers. 3. Difficulty in the production of homogeneous co-polymers. Applications 1. The method is used to get polymer for forming materials such as Polystyrene, Polyvinyl Chloride, Polyvinyl Acetate. 2. It is used for making plastic resins. All the thermoplastic resins are made by this technique.44 1.58 Engineering Chemistry 1.11 STRUCTURAL PROPERTIES AND USE OF BASIC POLYMERS 1.11.1 Structural Properties and use of PE Polyethylene is made from the polymerization of ethylene (or ethene) monomer. Polyethylene chemical formula is (C,H,),- H cH... He gH | | | | 1 I | | —c—c—c—c+C—C+C—-C— | | | | | | | | H H H H|H* H|H H n Fig. 1.18. Molecular Structure of Polyethylene Polyethylene is a lightweight, durable thermoplastic with variable crystalline structure. It is one of the most widely produced plastics in the world (tens of millions of tons are produced worldwide each year). Polyethylene is used in applications ranging for films, tubes, plastic parts, laminates, etc. in several markets (packaging, automotive, electrical, etc.). Main Characteristics and Properties of Polyethylene 1. Polyethylene Melting point: 120-140°C 2. Density of HDPE: 0.93 to 0.97 g/cm? 3. High Density Polyethylene Chemical resistance: ¢ Excellent resistance to most solvents @ Very good resistance to alcohols, dilute acids and alkalis @ Moderate resistance to oils and greases ¢ Poor resistance to hydrocarbons (aliphatic, aromatic. halogenated)Polymer Chemistry 1.59 >> 4. Continuous temperature: —50°C to +60°C, Relatively stiff material with useful temperature capabilities 5. Higher tensile strength compared to other forms of polyethylene Low cost polymer with good processability Good low temperature resistance Excellent electrical insulating properties Very low water absorption w oor PY 1.11.2 Structural Properties and use of PVC Polyvinyl Chloride (PVC or Vinyl) is a high strength thermoplastic material widely used in pipes and medical devices but list is endless. It is the world's third-most widely produced synthetic plastic polymer. Polyvinyl Chloride (PVC) is an economical and versatile thermoplastic polymer widely used in building and construction industry to produce door and window profiles, pipes (drinking and wastewater), wire and cable insulation, medical devices etc. It is the world’s third largest thermoplastic material by volume after polyethylene and polypropylene. Vinyl chloride monomer (VCM) is produced from the chlorination of ethylene and pyrolysis of the resulting ethylene dichloride (EDC) in a cracking unit. PVC (glass transition temperature: 70-80°C) is produced by polymerization of vinyl chloride monomer (VCM). H H H H Addition 2 we ceobmnersistaa | | es = se Ss c- Cc | ered H e H Cen Vinyl Chloride PolyVinyl Chloride C2H3Cl (CoH3CDn Fig, 1.19. Molecular Structure of PVC