—————— POLYMER AND PLASTICS units or parts) are macromolecules (giant ) formed by linking! joining together of a large Polymers (Greek Poly-many, M molecules of high molecular m number of small molecules (called monomers) Eg: Polythene is a polymer formed by linking together of a large number of ethane (C2H,) molecules. a (wsc-cte) POLYMERIZATION. —{-CHy ony Ethane (monomer) Polyethene, PE (polymer) Where ‘n’ is the degree of polymerization. Functionality of Polymer Functionality means the number of bonding sites in a monomer. For a substance to act as a monomer it must have at least two reactive sites or bonding sites. In an olefin, the double bond can be considered as a site for two free valencies when the double bond is broken, two single bonds become available for combination. ‘, / ‘\ i i \ i \ Hence ethylene can be considered bifunctional Classification of Polymers Polymers can be classified in the following ways: 1. Classification on the basis of source a) Natural polymers:- Polymers which are found in nature in animals and plants are called Natural Polymers. eg: Starch ( a polymer of a-D-glucose), cellulose (a polymer of B-D- glucose), proteins (polypeptides and polyamides), nucleic acid, natural rubber ( a polymer of cis-isoprene)ots nee — CH= POLYMERIZATION, 2.Methy-.3 butadiene Polisoprene (Rubber) tsoprene b) Synthetic Polymers:- Man made polymers are called synthetic polymers Eg: Polyethylene (PE), polypropylene (PP). polystyrene (PS), polyvinylchloride (PVC), nylon, terylene, Bakelite, 2. Classification on the basis of structure a) Linear polymers:- Polymers in which monomeric units are joined in the form of long straight chains, Eg: High density polyethylene (HDPE), nylon, polyesters. These polymers possess high melting point, density and tensile strength, due to close packing of polymer chain. a eee Se AR Fig: Linear chain polymer b) Branched chain polymers:- Branched chain polymers are mainly linear in nature, but also possess branches along the main chain. These polymers possess low melting point, density and tensile strength ‘compared to linear chain polymers due to poor packing off polymer chains in the presence of branches. Eg: Low density — (ore glycogen, amylopectin. wee yy aus Stans eee or Fig: Branched chain polymer ¢) Cross-linked or three dimensional network polymers:- It contains monomers molecules connected to each other by only covalent bonds.ment of indivatual monomer unite the pr They are plant molecules in which m: sence of strong cross Fig Cross-tinked polymer 3. Classification on the basis of their methods of aynthesis:- Based on the methods of synthesis. the polymers are classified into two groups Addition Polymers:- Addition polymers ate obtained by addition on method, which involves the repeat addition of monomers ed derivatives of ethane) to yield long chains, Their empirical formula is a) polyme: (unsatur same as that of monomers Eg Polyethylene, polypropylene, polystyrene, polyvinyl chloride ete 24 b) Condensation polymers:- Condensation polymers are obtained by a series of condensation reaction generally involving two monomers The condensation reactons usually results in the loss of small molecules like H20, HCI, NHs etc Eg Nylon-6, Bakelite, polyester 4. Classification on the basis of their behaviour when heated to processing temperature:- Polymeric materials are broadly divided into two categories on this basis: a) Thermoplastic polymers:- Thermoplastic polymers are linear, long chain polymers which can be soften on heating and hardened on cooling reversibly, ie their hardness is temporary property, subjected to change with rise or fall of temperature. Thus they can be processed again and again. Eg. Polythene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), nylons, polytetrafluoroethylene (PTFE or Teflon) etc. b) Thermosetting polymers (or thermosets):- Thermosetting polymers are those polymers, which during moulding (by heating etc) get hardened and once they have solidified, they cannot be soften, ie they are permanent setting polymers. Such polymers during moulding acquired three dimensional crossed-linked structures with predominantly strong covalent bonds. Thus a thermosetting polymer once moulded cannot be reprocessed. Eg: Polyester (terylene), Bakelite, epoxy-resin, melamine, urea-formaldehyde.5, Classification on the basis of physical state:- A polymeric material can be amorphous (eg: LDPE, rubbers. etc) or semi-crystalline (eg: HDPE, nylon, polyesters). and between _ thermoplastic Structural difference thermosetting polymers:- Thermoplastic possess comparatively weaker intermolecular forces and then there is no cross-linking. Consequently they are flexible, and can be easily moulded on heating, On the other hand there is excessive cross-linking in thermosetting plastics and different chains held through strong covalent bonds forming a three-dimensional network. Hence once set cannot be remoulded. On heating they first fuse to form hard mass and then burn. Comparison between thermoplastics and thermosetting polymers: Thermosetting polymers Thermoplastic Polymers 1. They soften on heating readi te They do not soften on he 2. They consist of long chain linear 2. Their set molecules have three- macromolecules. dimensional network structure, joined by strong covalent bond. 3. They are formed mostly by addition 3, They are formed by condensation polymerization. polymerization. 4. By reheating to a suitable 4, They retain their shape and structure, temperature, they can be softened, even on heating. Hence they cannot be reshaped and thus reused. reshaped and reused. 5. They are usually soft, weak and 5. They are usually hard, strong and less brittle. more brittle. 6. They can be reclaimed from 6. They cannot be reclaimed from wastes. wastes. 7. They are usually soluble in some 7. Due to strong bonds and cross-linking, organic solvents. they are insoluble in almost all solvents.Polymerization:-Itis the process by which simple (monomers) molecules join together to form very large (polymer) molecules. Hence the system of large molecular weight polymer is termed as polymerization There are three different ways of doing polymerization: (a) By opening a double bond: a ( Hzc=cH,) —POLYMERIZAT es oy set Ethene (monomer) Polyethene Where ‘n’ is the degree of polymerization. (b) By opening a ring: oO Oo Valerolactone fopoutclt— (c) By using molecules having two functional groups a Hooc-{cH} COOH, +n Hy—{-CHy } NH Adipic acid Hexamethylene diamine —— tou ft Lon ie Mechanism of addition polymerization Polymerization reaction involves union of two or more small molecules to form a large molecule called polymer. Polymerization of ethylene and its substituted compel, CH2=CHX can be carried out by using any of the following mechanism:- 1. Free radical polymerization mechanism:- It involves the following steps (a). Initiation step:- It is considered to involve two reactions. The first one is the production of free radical usually by homolytic dissociation of an initiator (or catalyst) to yield a pair of radicals R*.| ———- 28 Initiator The second part of initiation involves the addition of these radical to the first ‘monomer molecule to produce the chain intiating species Mr. R + M My Free radicals Monomer molecules ‘Chain initiating species Thus the polymerization of monomer, H,C=CHY takes in the form:- M Roo+ Hc=cHy — > pc — Y Free radicals Monomer molecules Chain initiating species (The radical are is often referred as an initiator radical or a primary radical). (b). Propagation Steps consist of the growth of My’ by successive addition of large no. of monomer molecules according to equation Mi a a a Cha inating species CORin general term; My + M —* Maat (c). Termination steps: At some point the propagating polymer chain stops growing and terminates i) Coupling or com! ioe er —o— 6 + bo Seale, or —g—G—cr — Y § YY ii) Disproportionation 4, -Diseoeatonston. oy, dy lo x2. Cationic mechanism of polymerization: Itinvowes the following steps A ys Hc==cH a = ¥en x x an acid Anew eat on (Acat ion) (Carbocation) } 8. Propagation: ‘ ° \ Hy cH cH CHG k ‘Anew eation (Carbecaton} C. Termination: \ 2° yon, —ch, —2_- y +H, —cHy CHa GHZ (An anion) | k } Methods of polymerizatio' 1) Addition polymerization: Polymer synthesis by addition polymerization has the ‘same empirical formula as that of monomer. No molecule is evolved during polymerization and the polymer is an exact mutiple of the original monomeric units. (nop) eo ES {SG=Substiuent group) * 2) Condensation polymerization: It takes place by the condensation of two different bi or poly functional monomers having functional groups which have Sffnty for each other, eg. ~COOH and -OH or ~COOH or -NH2 carryingmonomers undergo condensation polymerization. It is always accompanied with the elimination of small molecules like HzO, HCl etc. m HOOC-{cHs} COOH, + mthN-{-CHe }— Nie Adipic acid Hexametnylene diamine Oo -2nH,0 I Row Ht. aa. —cH,—c—N-{ Hz} —N +4 fore}, 8 Nylon-6,.6 Molecular weight of polymer All the molecules of the polymer sample don't have identical molecular weight, hence polymers are polydispersed. This is a consequence of the fact that in a polymerization reaction, the length of the chain formed is determined entirely by random events. In condensation reaction it depends on the availability of a suitable reactive functional growth and in addition. Number average molecular weight (,): It is define as the total weight (w) of all molecules in a polymer sample divided by the total number of moles present: w _ DN: Mn = N= ON Where Ais the number of molecules of molecular weight M.. Weight average molecular weight (#,): When the molecular weight is averaged according to the weight of molecules of each type, M, is obtained. It is determined by the light scattering measurements and h the methods depend on the weight of the sedimentation-equilibrium methods. Bot! molecule present. The weight average molecular weight M,, is define by — _UN MP Mw = NM, Where A, is the no of molecules of molecular weight Mi. Crystallinity in polymers: Even a polymer with regularity of molecular structure doesn't entirely in crystalline form. This is because of their large size . As solidification begins the viscosity of the polymer rises and the molecules find more and more difficult in arranging there long chains in the regular pattern needed for crystal formation. Infact , polymers haveions of crystallin eretsinien previde ae crystallites embedded in amorphous material, polymeric material. The densit and amorphous region provides flexibility to the non-crystalline polymer scam - the crystalline polymer is greater than that of a Of more efficient packing of the former. fom density measur packing a y Tinta aents: It is possible to determine the degree of (or percentage) crystallinity by using the following formula Percentage crystallinity R te :) x 1 y R/ (RP? Wheref2'= density of perfectly cryslline polymer lensity of amorphous polymer ; lensity of a specimen whose % crystallinity is to be determined Biopolymers: The polymers present in living matter, animals and plants are termed as biopolymers. Eg: polysaccharides (carbohydrates), protein, nuclei acid and natural rubber. Broadly speaking there are four types of biopolymers viz: Biopolymers Carbohydrates Protein Nucleic acid Natural rubber (polynucleotides) (cis-1,4-polyisopregfne) (polysaccharides) (polyamides) Degradation of polymers: a) Oxidative degradation: It is caused by contact with oxidising agents, prolonged application of excessive heat etc. It results in embrittlement and stress cracking. Deterioration in electrical insulation properties and loss of elasticity. It affects most thermoplastics to varying degrees, in particular PE, PP, PVC, nylons and unsaturated polymers like rubbers etc. radation: It causes adverse changes in mechanical and 0°C in the b) Thermal deg electrical properties of PVC, when PVC is heated to above 15 presence of oxygen. The dehydrochlorination process results in the formation of conjugated polyene. chitecnoler eh, eth es etek, Gh Aye —les. & de & Pelyyrnagl Deco (PPP {= CH check —Ch = Page’Commercially important thermoplastics and thermosets: 1) Polyethylene:- It is also known as polythene. It is prepared by the addition polymerization of ethylene (CH,=CH,). There are different types of polyethylene: i) Low density polyethylene (LDPE): Preparation: It is prepared by polymerizing ethylene at high pressure 1000-5000 atm and at 250°C in the presence of free radical initiator (Oz). MMH Aah, —_[er- Sedeahn Et el ou dics APE ' uuthtalet Properties: a) During the propagation steps large no of chain transfer reactions takes place resulting in the formation of branched structure. These branches are mainly short chain. These branches don't allow the molecules to pack efficiently and hence its density is low. b) Dus to low density, crystallinity of LDPE is low (around 55%). ¢) As itis non-polar polymer, there are no strong intermolecular forces. 4) Itis chemically inert and has good chemical resistance. €) Ithas excellent electrical insulator properties. f)_Itis tough and flexible even at low temperature. ii) High density polyethylene (HDPE) Preparation:- HDPE can be made by following two methods: a) Using Zeigler-Natta catalyst, ethylene is polymerized under 6-7 atmospheric pressure at 60°-70°C in the presence of { TiCly+Al(CzHs}} or catalyst. A _ eee Noda "I Rhy Te 8 b) Using supported metal oxide catalyst, like CrO; supported on silica~ alumina, ethylene is polymerized at 35atm pressure and a temperature of 62-200°C. Properties: a) HDPE molecules are linear and hence it has high densty and more percentage crystallinity (80-90%). b) Softening temperature of HDPE is also higher than LOPE. ¢) HDPE has excellent chemical resistance. 4) It has excellent electrical insulation property. (0.95-0.97g/cm*)2) Polyvinylchloride (pyc). PVC is made by addition 5) a) Rigid Pvc; | P°YMerizatign, Pf Preparation: {tj “I'S of two types. is water) in the ade by yj Presence of gM! chlorid smulsion of it Poronide as catayarse fe (in the form of emulsion of it in a ‘all amount of bi int of benzoyl peroxide or hydrogen Pressure in an autoclave. @. mea, sate etymeted . SN Voy} Mil Yeseod 2 Eon i b) Plasticized Pvc: Pelpcmyl Dero, Brpaaton ioe ead PVC) It is obtain by a k phthalate), "Y adding plasticisers such as DOP (dioctyl )-eibuty phthalate, crest phosphate tc to rgd PVC. Qn: 3) Polystyrene: Preparation: Polystyrene is Nr in the presence of bensoyt ee Pare bY fee radical polymerization of styrene Peroxide as catalyst. = me, = Retyreas 3 H2=H—t,), emeerlon, fa. oe + aye Ie Properties: a) Because of the presence of bulky phenyl group , packing of PS chains is not efficient and hence it is an amorphous polymer. b) Due to chain, stiffening effect of the benzene ring , PS is hard but brittle. c) Being a non-polar amorphous polymer, its softening temperature is low ( 82-100°C) 4d) As itis non-polar, it has low tendency for moisture absorption. or of 4) Polytetrafluoroethylene (PTFE) or Teflon: Preparation: Teflon is prepared by the polymerisation of tetrafluoroethylene under pressure in the presence of benzoyl peroxide as catalyst GPedyperitele chek F, es cole, Eun, AChaeZ a mn Ta Toner two step zig zag structure with the fluorine atom packing tightly in ef keleton. Due to the presence of highly , ‘carbon ~ carbon si a spiral around ee tom, there are very strong attractive forces between oe ae ie yore trong attractive frees are responsible for jifferent change. a) High Density b) Chemical inertness over @ wide temperature range. SP aby fins nef ise Stolen Pelrfadre fre unter (PTE)EE OOO_ 3) Known adhesive characters d) Excellent toughness ang heat regi istance conDUGTING POLYMERS yer which an conduct electyi A icity jg a it fe trduting Polymers can be classitieg j y is termed as a conducting polymer into nh types: Brelacag Fobyme> | oh . | . Lrinsteny Caden alg Palomo tobaig yr a v L » Qrekodik Clore 4 : ed elyed —— Covebachry wy patie ot ig pss 4) intrinsically conducting polymers: These polymers have extensive conjugation in the backbone which is responsible for conductance. These are of two types: 2)Conducting polymers having conjugate r-electrons in the backbone: Such polymers contain conjugate r-electrons in the backbone which increase the conductivity to a large extent. This is because, overlapping of conjugate T- electrons over the entire backbone results in the formation of valance bands as such as conduction bands which extends over the cationic polymer molecule. The valance band and conduction bands are separated by a significant band gap. Thus electrical conduction could occur only after thermal or photolytic activation of electrons to give them sufficient energy to jump the gap and reach into the lower level of the conduction band Eg A. CHEcn be evn ee ¥ Qs Oa H 4 o-2 4 Pely Pyvole b) Doped Conducting Polymer: In comparison to conventional polymers the conducting polymers of type (a) can be easily oxidised or reduced as they dang orn potentials and high electron affinities, Their conduetiviies can be increased by creating positive oF negative charge on polymerpone by oxidation or req pac itis reformed to as dope ey, analogy with som! conductor wea loping and is of following two types : | doping: It is done by oxidatioy i InP Lewis acd oF with odin " rocess conducting posers of Pe @) i apour or iodine in CCl. ~ x ‘ect doin, pro ut" CoWet kt A = D0 | 7 Cou Peale. ewes aie on payers yee et CL xt 2EQ; —> Ceyr®p ? + Fedo — 5 eux + 9 CH) Fey 2 Ceara ater: ee ea eo exsdelin) _ Pescebjoe 4, [edn www SS = polars —e tents) [hy > 5 : ee a Bifaloces Caicobin) Ceege in ot wh eS) - @® x ROS Sere ta Be te: Aw te , ‘ 1 te ieeapsirnselin process. For ths corded potyrl 4 ‘hyp Gy Sebnated wth bos “hese, C8) ORe acelin rophttabile —> Condy 8” Myanb fen — fsa it ar dapesk peyacelyer— - & 7 © Ecorse) — > ¥* cert P + Gole