Module POLYMERS Weightage : 18 Marks Introduction: Definition- Polymer, polymerization, Properties of Polymers-Molecular weight (Number average and Weight average), Numerical problems on. molecular weight, effect of heat on polymers (glass transition temperature), Viscoelasticity, Conducting Polymers, Classification-Thermoplastic and Thermosetting polymers; Compounding of plastic, Fabrication of plastic by Compression, Injection, Transfer and Extrusion moulding, Preparation, properties and uses of PMMA and Kevlar. Topics: 5.1 Introduction : Classification, Types of Polymerization 5.2 Thermoplastic and Thermosetting Plastic 5.3 Compounding of Plastic 5.4 Fabrication of Plastic by Compression, Injection, Transfer and Extrusion Moulding 5.5 Preparation, Properties and Uses of Phenol Formaldehyde, PMMA, Kevlar 5.6 Properties of polymers — Molecular weight 5.7 Effect of heat on polymers 5.8 Conducting polymers 5.9 Graded Questions Galo Kir 9Eng’ mpt dK Vg" s @o wi 6/ 3 4/ 0 74 28 Mf dsteRnkdc-Module 5: Polymers | 69 5.1 INTRODUCTION : CLASSIFICATION, TYPES OF POLYMERIZATION INTRODUCTION The word QPMENFS is derived from Greek words polys (= many) & meros (parts/units).. ‘A polymer is a large molecule which is formed by repeated linking of small molecules called as NPOPNFST/! -A-A-A-A-A-A- (Apolymer) {where A is a monomer] It can be also represented as : —~A-B-A-A-A-B-B-A- [where A, B - monomers] Monomers : (Definition) Monomers are simple small molecules which combine with each other under specific conditions of temperature, pressure and catalyst to form a big molecule. called polymer. Polymers are ‘macromolecules’ (giant molecules of molecular masses). Polymer : (Definition) Polymer is a big molecule, formed by the combination of a large number of monomers under specific conditions of temperature, pressure and catalyst Examples : Monomer Polymer CH; = CH2 Ethylene Polyethylene (PE) (CH, = CHCHs Propylene’ Poly propylene (PP) CcHs — CH = CHe Styrene Polystyrene (PS) CoHsOH HCHO, Phenol Forrlaldehyde Phenol Formaldehyde (PF) NHe — CO = NH2 HCHO Ure Arb rts Urea Formaldehyde (UF) (Commonly used of polymer materials are Plastics, Fibres, Elastomers, Adhesives). 5.1.1 Classification of Polymers Polymers are classified on the basis of : (a) The sources (b) Chemical composition (c) Method of polymerisation (Method of preparation) (d) The structure of polymers (a) Classification of polymers based on the sources : 1. Natural polymers : e.g., rubber, proteins, cellulose, etc. 2. Semi-synthetic polymers : e.g., cellulose acetate, nitrocellulose, etc. 3. Synthetic polymers : They are divided into three types : i) Synthetic Elastomers: e.g. Buna-S rubber, Neoprene rubber, Silicone rubber, Nitrile rubber, Polyurethane, etc. ii) Synthetic Plastics : They of two types A. Thermoplastic or Thermosoftening plastics e.g. : polyethylene , polystyrene, polyvinyl chloride, etc. B. Thermosetting or Thermohardening Plastics .g. : phenol formaldehyde, Urea formaldehyde, etc. C. Synthetic Fibres : e.g. : polyesters, polyamide, etc.70| Vidyalankar : F.£.- Chemistry | (b) Classification of Polymers on the basis of Chemical Composition (i) Organic Polymers : Organic polymers along with carbon atoms contain, hydrogen, oxygen, nitrogen, sulfur, halogen atoms. e.g.: PVC, PE, PS, etc. (ii) Hetero-organic Polymers : These are the compounds whose chains are composed of carbon atoms and hetroatoms like Si, Ti, etc. an tf NB NBN NB NSN Q Q Q Q Polysiloxanes Polytitoxanes (ii) Inorganic polymers : These are polymers which do not contain carbon atoms. e.g. t fF res GGG Polysilanes (©) Classification of Polymers on the basis of method of Polymerisation (i) Addition Polymers or Association Polymers These are of two types 1. Homopolymers : ¢.g.: PE, PS, PVC, etc. 2. Copolymers: e.g. : Styrene — butadiene, etc, (ii) Condensation Polymers : Condensation polymers are prepared by condensation polymerisation. e.g. Phenol formaldehyde, Urea formaldehyde etc. (d) Classification of Polymers on the basis of structure The polymers can have different structures as follows. Linear structure : The different monomers are linked in a linear or straight chain fashion. The intermolecular movement is comparatively easy as the polymer chains are held together by secondary Van-der-Waal's force of molecular attraction. e.g. : Polyethylene, polypropylene ete. Polymer secondary Van der waal’s bonds Polymer Branched structure : The polymer has linear chains alongwith branching. The intermolecular movement is restricted here. e.g. : Glycerol etc. GN—BG—BG—BG-NG Where 3 functional groups are present. NGModule 5: Polymers _| 71 Cross linked structure : The polyfunctional monomers possess the cross linked structure, They show a 3D network with maximum linkage & thus intermolecular movement is almost impossible. e.g. : urea formaldehyde (Bakellite) etc. 5.1.2 Degree of Polymers The number of repeating units of monomers in a molecule of polymer is known as degree of polymers. There may be hundreds, thousands, ten thousands or more monomers units present in a molecule of polymer. Most of the polymers usually fall into 5,000-200,000 molecular weight range. Polymers with high degree of polymerisation are known as high polymers. For a high polymer minimum degree of polymerisation is 100. 5.1.3 Polymerisation The process of formation of a polymer by the union of a large number of the similar or different types of monomers with or without elimination of any compound is called polymerisation. n (CH = CHa) monomers) Polyethylene CS ae Ethylene (polymer) Types of Polymerisation : Following are the types of polymerization. 1. Addition polymerisation: These are two types (i) Homopolymerisation (ii) Copolymerisation 2. Condensation Polymerization 1. Addition polymerization : It is a type of polymerisationin which a large number of similar and different types of monomers combine with each other to form a big molecule of polymer without elimination of any compound. During polymerization, rearrangement of molecules takes place where one of the double bonds breaks and-each carbon atom acquires one free valancy. A large number of such unstable molecules combine with each other as shown in reaction forming polymer-polyethylene. io {oa Toa a aa OY ele ede usados Ethylene monomer Molecular rearrangement —_—_-Polyethelene (Polymer) (i) Homopolymerisation : It is a type of addition polymerisationin which similar types of monomers combine with each other forming a polymer without elimination of any compound. e.g. Polyethylene. (ii) Copolymerisation : It is a type of addition polymerisationin which different types of monomers combine with each other forming a polymer without elimination of any compound.72| _Vidyalankar : F.£. - Chemistry | e.g. : Formation of Styrene ~ butadiene Polymer GR ~ S rubber. CH=CH, nCH, =CH-CH=CH,+n n— CH, ~ CH= CH~ CH, ~ butadiene Styrene molecular rearrangement ~CH~ CH, - — CH — CH, ~ CH; ~ CH = CH ~ CHp— +n > Polymer n molecular féarrangement Styrene — butadiene 2. Condensation Polymerisation : It is a type of polymerisationin which a large number of similar or different types of monomers combine with each other forming a polymer with the elimination of some simple compounds like HO, HCl, etc. e.g. : formation of urea formaldehyde Nis HN - GH.08 LG +2080, 9 4 é-0 fine tormataenyoe HN —cH.on trea dmetryiol ies “Bn= enforr IN - cK “N= CHe= N= CH : -HOH : c-0 + c=0 HOH, c-0 c-0 = 1 -N-CH.—N-CH.- urea formaldehyde Urea and formaldehyde when heated together undergo condensation polymerisation and form urea formaldehyde with elimination of water molecules. 5.2 THERMOPLASTIC AND THERMOSETTING PLASTIC Plastics are high molecular weight, organic materials capable of being shaped into any form by the application of heat and pressure. Plastics are high polymers. Plastics have the property called as ‘plasticity’, Classification of plastics There are two types of plastics 1. Thermo-softening plastics (Thermoplastics) 2. Thermosetting plastics (Thermohardening plastics)Module 5: Polymers _|73 1. Thermosoftening Plastics (Thermoplastics) : Thermoplastics are those which becomes soft on heating and hard on cooling. Hard Heat, Soft —teat_, Soft —8°, Hard i.e., their hardness is a temporary property subject to change with rise and fall of temperature. Thermoplastics becomes soft on heating and remain soft as long as they are hot. On cooling they regain their original rigidity and hardness. Repeated heating and cooling do not alter their chemical nature, because changes involved are purely of physical nature. The term ‘resin’ and ‘plastic’ are synonymous in the case of thermoplastics because chemically there is not difference between them. Thermoplastics are prepared by Addition Polymerisation. They are long chain linear compounds with negligible number of cross-links. 2. Thermosetting Plastics or Thermohardening Plastics : Thermosetting plastics are those which during moulding due to heat get hardened and.once they are solidified, they cannot softened. They are permanent setting plastics. Such plastics, during moulding acquire 3-dimensional crossed linked structure with large number of strong covalent bonds. These bonds retain their strength even on heating. On prolonged heating charring is caused. The term ‘resin’ and ‘plastic’ do not denote the same material chemically in case of thermosets and hence, should not be used interchangeable. Qt Ans.: Distinguish between thermoplastic and thermosetting polymers. [D-16; M-17] ‘Thermoplastics Thermosetting plastics , |They are formed by Homo and Co-polymerization. They are formed by Condensation Polymerization 2, |They consist of a tong chain linear polymers with a limited number of cross-links R-R-R-R-R I -R=R-R-R-R- | -R-R-R-R-R- lwhere R — monomers. They consist of a network of chains joint together by cross-links. | | tod | R-R-R-R-R | | lod | IHR - R-R-R-R- | I ee] | -R-R-R-R=R= Ele | where R — monomers. 3. Inter molecular forces are comparatively weak, because they are linked by weak bonds. Inter molecular forces are comparatively strong, because they are linked by strong bonds. 4, [The weak bonds easily break up by heat and pressure. Thus they become soft on heating and hence ican be reshaped or reused. The strong bonds do not break up by heat and pressure. Thus they do not become soft on heating and hence cannot be reshaped or reused. 5. [They are soft, weak and less brittle. They are hard, strong and more brittle. 6. [They can be reclaimed from wastes. They cannot be reclaimed from wastes.74) Vidyalankar : F.E. - Chemistry I 7. (Usually they are soluble in some lorganic solvents, due to weak bonds land negligible cross links. They are insoluble in almost all lorganic solvents due to strong bonds land cross links. [They have low molecular weights | They have high molecular weights 0} 2] e.g. : Polyethylene ; Polystyrene; polypropylene etc. fe.g. : Phenol formaldehyde ; Urea formaldehyde etc. 5.3 COMPOUNDING OF PLASTIC Qt Ans.: Write a note on compounding of plastic. [M-17] To impart specific properties to plastics, they are mixed with certain substances. This process of mixing is known as compounding of plastics. Compounding improves the properties as well as rectifies the flaws if there are any 1. Resins : It is the main constituent of plastic. It is actually the binder which holds the constituents. of plastic together. The type of resin decides which method of fabrication has to be used. Plasticizers :These materials are added to increase the plasticity and flexibility of plastic. It also reduces the brittleness and softening temperature of plastic. e.g. Camphor, Tricresyl phosphate. The plasticizer molecules occupy the positions in between the polymer molecules and reduce the force of intermolecular attraction. This helps in easy sliding of molecules of polymer which increases the flexibility of polymer molecules. ——_SS= Ss SSS SSS SSS SSS Unplasticized polymer Fillers: The main job of filler is : to reduce the cost of plastic to reduce the flexibility (to make it stiff) to decrease the shrinkage during moulding to increase hardness and tensile strength. Commonly used fillers are saw dust, cotton, paper pulp, c-black, mica, asbestos, clay, quartz, marble powder, metal powders, metallic oxides etc. The fillers can be added upto 50%. Lubricants : Lubricants are added to plastics during moulding to make moulding easier and impart a glossy, flawless finish to the produce. They also prevent the plastic material from sticking to the mould. e.g. : waxes, petroleum lubricating oils, vaseline, soaps of stearates, oleates etc. Pigments : Pigments impart colour to the plastic products. They are generally organic dyes or opaque inorganic substances. Some of the pigments are Plasticized polymer ultramarine > blue CaCOs, ZnO-> white Antimony Sulphide —» Crimson red C-black-» black Chromium trioxide » Green Iron oxide >» RedModule 5: Polymers _| 75 5.4 Qt ANS: 5.4.1 Q2 Ans.: 6. Stabilizers : The main function of stabilizers is to improve the thermal stability of plastic during moulding. @.g.: PVC shows a tendency to undergo decomposition and discolouration at the moulding temperature. Some examples of stabilizers are : a) lead chromate, lead silicate, lead carbonate etc. used for opaque moulding, b) stearates of lead, cadmium, barium are used for transparent moulding. 7. Catalysts or Accelerators : These are added to accelerate the process of moulding and polymerisation. e.g. : Benzoyl peroxide, hydrogen peroxide, ZinC oxide etc. 8 Antioxidants : The oxidative degradation of polymers can be prevented by addition of antioxidants. e.g. : Phenyl 6 - naphthylamine, diphenyl. p-phenylene etc. FABRICATION OF PLASTIC BY COMPRESSION, INJECTION, TRANSFER AND EXTRUSION MOULDING What are the various methods used for fabrication of plastic? To give desired shape to a plastic is known/as fabrication or moulding of plastic. The method used for moulding of plastics depends upon 1. Type of plastics or resins used. (.e., Thermosoftening or Thermosetting Plastics) 2, The shape of article to be made. The Methods for fabrication of Plastics are : 1. Compression Moulding 2. Injection Moulding 3. Transfer Moulding 4. Extrusion Moulding Compression Moulding Explain the compression moulding. Compression Moulding Compression moulding method is applied to both Thermoplastics and Thermosetting plastics. But mostly it is used for Thermo-setting platics In compression moulding : 1. Raw materials of the right composition are placed between the two half pieces of mould. 2. The mould is carefully closed. 3. Then, the mould is subjected to high pressure of the order of 100 - 500 Kg/om®, and high temperature of the order of 100 - 180° C. 4, Curing : In case of Thermoplastics curing is done by cooling. In case of Thermo-setting plastics curing is done by heating. 5. After curing mould is opened and plastic article is taken out76| Vidyalankar : F.£. - Chemistry | Nowadays automatic compression moulding machines are also available. te ” Compression molding for thermoplastics: (1) charge is loaded, (2) and (3) charge is compressed and cured, and (4) opening the mold halves and removing the part from the cavity, 5.4.2 Injection Moulding Q.2 What is fabrication technology? Mention various moulding techniques and explain injection moulding with the help of diagram. [D-16] Ans.: Injection Moulding Plastic offer Powder] ie SS: Piston Heater mould Injection Moulding of Plastic : Injection moulding is used for Thermoplastics. In Injection moulding; 1. Raw materials of the right composition is fed into a cylinder heated by electrical heater. 2. Due to high temperature in cylinder plastic power gets melted and almost becomes liquid. 3. Liquid plastic is injected (forced) under high pressure by a piston plunger, through a heated nozzle at a controlled rate into a cold mould, which is tightly locked by means of a screw arrangement. 4. Temperature maintained near nozzle is between 130-260°C. 5. Curing : The mould is kept cold, so that hot thermoplastic gets cured. 6. Once the curing is over, mould is opened and article is taken out. Thermoplastic material used in injection moulding are; Polystyrene; Collulose-acetate. Articles prepared by injection moulding are; Ball pens, telephone, buckets, dust bins, flower pots etc.Module 5: Polymers _| 77 5.4.3 as Ans.: Transfer Moulding Describe transfer moulding in polymers. Transfer moulding is a modification of injection moulding for the use of Thermosetting plastics. In transfer moulding : ib 2. 3. 5. 6. Raw materials (Compound plastic powder) of right composition is fed into a cylinder which is heated by electrical heater. Here, raw material is heated to minimum, so that it gets plasticised. The plasticized material is then injected (forced) under high pressure by a piston plunger through anorifice at a controlled rate into a hot mould which is tightly locked. Due to very great friction developed at orifice, temperature of material rises to such a high extent that the plastic powder becomes almost liquid, and so it flows quickly into the mould. Curing : Mould-is heated upto the curing temperature (temperature required for setting) Once the curing is over, moulded article is taken out mechanically. This method is used for making Thermo-setting plastic articles of complicated shape and delicate design. le Piston Pre-heater Moulding powder in « plastic state Orifice Moulding powder in >> cavity Upper part of Hinge mould |< Lower partof mould78| Vidyalankar : F.E. - Chemistry I 5.4.4 a4 Ans.: 5.5.1 Qt Ans.: Extrusion Moulding What is meant by fabrication of plastics? Explain Extrusion moulding with the help of neat diagram. Plastic Powder Electric Heater —_ —— Hopper comin a ZZ y ———h, L Conveyer belt Z| Fvid plastic ‘Screw conveyor| Extrusion Moulding Extrusion moulding is mainly used for continuous moulding of Thermoplastic materials. This method is used for manufacture of Thermoplastic articles of uniform cross- section like; tubes, pipes, rods, sheets, strips, metallic wires, cables, etc. are also covered by plastic using this method. In Extrusion moulding 1. Raw material (compounded plastic powder) of the right composition is forced by a screw conveyer into a heated chamber. 2. Inheating chamber plastic powder is heated to melting. 3. Liquid plastic is forced through a die of required shape 4, Article which is coming out of the die is cooled either by atmospheric exposure or by blowing air or by spraying water, as it is caried away by a long conveyer. PREPARATION, PROPERTIES AND USES OF PHENOL FORMALDEHYDE, PMMA, KEVLAR () PMMA (ii) Kevlar Polymethyl Methacrylate (PMMA) Explain preparation methods & uses of PMMA. [D-16] The monomer used in methyi methacrylate (an ester of methyl acrylic acid is produced from acetone). Polymethyl methacrylate is obtained by polymerization of methyl methacrylate in presence of acetyl peroxide or hydrogen peroxide. It is an acrylic polymer. q oi Free radical vinyl fi n r= —___ =o Polymerization a / / 9 \ CH CH; Methyl methacrylate Poly Methyl Metha acrylate5.5.2 Q2 Ans.: 5.6 Module 5: Polymers _|79 Properties : 1. It is colourless, transparent, hard and fairly rigid material. 2. Itis amorphous because of the presence of bulky side groups in the molecules. 3. It has high softening point of about 130°C to 140°C and becomes rubber like a temperature above 65°C. 4, Ithas high optical transparency. Uses : 1. Its sheets are used for signs, glazing skylights and decorative purposes. 2. Itis used for making artificial eyes, emulsion, paints, TV screens etc. Kevlar Write synthesis, properties and applications of Kevlar. [D-12] Kevlar is an aromatic polyamide similar to nylons, but with benzene rings rather than aliphatic chains linked to the amide groups —CONH-. It is prepared by polycondensation between aromatic dischloride and aromatic diamines, e9., n[ coe Opcoe] + » [Ont] Terephthalicse dione | 2 PrAmincanline : | HCL gl Alamabencon) Lotto! Kevlar Properties : Kevlar is exceptionally strong (5 times stronger than steel and 10 times stronger than Al on a weight-for-weight basis). It has high heat stability and flexibility. The unique properties of Kevlar are due to the delocalized bonding which causes the benzene rings to be inflexible. Therefore, Kevlar is far more right than nylons. The high electron-density in the chains of Kevlar also results in relatively stronger van der Waal intermolecular forces between neighbouring polymer molecules. Uses : Kevlar is used extensively in the aerospace and aircraft industries, car parts (such as tyre, brakes, clutch linings, etc.,) ropes, cables; protective clothing, bullet-proof vests, motorcycle helmets and other high performance materials. PROPERTIES OF POLYMERS > MOLECULAR WEIGHT Polymer molecular weight is important because it determines many physical properties. Some examples include the temperatures for transitions from liquids to waxes to rubbers to solids and mechanical properties such as stiffness, strength, visco-elasticity, toughness and viscosity. It molecular weight is too low, the transition temperatures and the mechanical properties will generally be too low for the polymer material to have any useful commercial applications. Unlike small molecules, however, the molecular weight of a polymer is not one unique value. Rather, a given polymer will have a distribution of molecular weights.80] Vidyalankar : F.E. - Chemistry I Since a polymer is generally a mixture of molecules of various molecular weights and molecular sizes, we can vislualize a molecular weight distribution. Therefore, for polymers we should not speak of a molecular weight but buf sbht!n pthite! xfjtiu There are many ways, to calculate bo average molecular weight, depending on how the average molecular weight for a given distribution of molecular weights is defined. Different xbzt to define molecular weight of polymers are as follows: 1. Mn: Number Average Molecular Weight Weight Average Molecular Weight : Viscosity Molecular Weight Mz : Zaverage Molecular Weight 1 Z= 2. 3. 4. The distribution will depend on the way the polymer is produced. It-we plot Uf! molecular weight distribution for a polymer and indicate the locations of the various molecular weight average we have discussed, here is what we would see: Mv Mw ry Mz. aignnfol Wi Low Mot, wi Fig. : Distribution of molecular weight of a polymer From the distribution graph we see the Z-average is located at the extremely high molecular weight end of the distribution and the weight average slightly lower down in molecular weight. The viscosity average is very close to the weight- average. The number average is located closer to the low molecular weight end of the distribution. It: may be noted that the Z-average is always greater than the weight-average which in tum, is greater than the. viscosity-average, which is always greater than the number-average molecular weight. As we go in this series from number-to viscosity-to weight - to Z-average molecular weight, the large molecules in a polymer sample become increasingly important. Number Average Molecular Weight Consider a property which is only sensitive to the number of molecules present, a property that is not influenced by the size of any particle in the mixture. The best example of such properties are the colligative properties of solutions such as boiling point elevation, freezing point depression, and osmotic pressure. For such properties, the most relevant average molecular weight is the total weight of polymer divided by the number of polymer molecules. This average molecular weight follows the conventional definition for the mean value of any statistical quantity. In polymer science, it is called the Number Average Molecular Weight.Module 5: Polymers _| 81 Let Nj be the number of polymers with molecular weight M,. Then the total weight of all polymers and the total number pf polymer molecules are as follows : NM, yw Total Weight =. =1_ 2N Total Number = )°N, a Therefore, the number average molecular weight is =NM, ij. - TotalWeight = _ "Total Number The term N/ SN; is physically the number fraction of polymers with molecular weight M,. If we denote number fraction as X; (i.e. mole fraction) the number average molecular weight is My = =XiM, Weight Average Molecular Weight Consider the polymer property which depends not just on the number of polymer molecules but on the size or weight of each polymer molecule. A classic example is light scattering. For such a property we need a weight average molecular weight. To derive the weight average molecular weight. To derive the weight average molecular weight, replace the appearance of the number of polymers of molecular weight i or Ni in the number average molecular weight formula with the weight of polymer having molecular weight i or NiMi, The result is Ha = nine / SNM By noting that NIM/NIM; is the weight fraction of polymer with molecular weight Mi and w, an altemative form for weight average molecular weight in terms of weight fractions. Mu = Swim, 7 SNM we, w= SNM” EW Comparing this expression to the expression for number average molecular weight in terms of number fraction we see that Mn is he average Mi weighted82| Vidyalankar : F.E. - Chemistry | according to number fractions and that M,, is the average Mi weighted according to weight fractions. The meanings of their names are thus apparent. The weight average molecular weight is determined by the Light scattering, Small Angle Neutron Scattering (SANS) and Sedimentation velocity. 5.7 EFFECT OF HEAT ON POLYMERS 5.7.1 Melting and Glass Transition Phenomena Q.1_ What is glass transition temperature? State the factors affecting it. Ans.: Glassy stato | Viscoelastic state | Viscofluid state \ | _— Temperature H T! 1 Tm 1..Rubber or plastic when cooled upto certain temperature, it becomes hard and brittle and it breaks like glass.on application of stress. 2. Glass Transition temperature is defined as the temperature below which the polymer becomes hard, brittle and glassy and above which it is softer and flexible. It is denoted as Ty. €.9. Polyethylene - Ty - 125°C, Polyethylene ~ T, 100°C, Nylon 6 - Ty 50°C 3. The hard and brittle state is the glassy state and soft — flexible state and rubbery or viscoelastic state and on heating further, the polymer becomes a viscous liquid and it is called as viscofluid state Amorphous polymers do not possess melting points, but softening point. At low temperatures, polymers exist as glassy materials. If the temperature is increased, Polymer softens and becomes more flexible. This happens at the glass transition temperature (Tg). After this, crystalline and amorphous thermoplastic polymers behaves differently. (a) Amorphous polymers Glass | — Rubber Gum Liquid i Increasing ae temperature transition temperature (b) Crystalline polymers Crystalline and Seevtegons + _ Flexible thermoplastic Liquid 1 Increasing Glass Melting "emperature transition Point temperature Fig: Effect of temperature changes on amorphous and crystalline polymers. Notice that amorphous polymers do not possess any clear melting point.Module 5: Polymers | 83 5.8 Factors affecting Ty Ty increases as the molecular weight increases. T, decreases with increase in flexibility in chain of polymer. Ty increases as the degree of cusslinking increases. Ty decreases by adding a plasticizer to polymer. Ty increases as the intermolecular forces of attraction increases. gaeNe CONDUCTING POLYMERS 5.8.1 Electrical Properties of Polymers 1. 2. Common polymers are used as insulators in electrical and electronic applications. If a plastic is compounded with metal powder, it becomes a conducting material but here it is not the plastic that conducts but the metal powder. 5.8.2 Structural Requirements 1. 2. 3. Qt For a polymer to. start conducting electricity, it should have free-electrons as. in metals The presence of relatively free electrons is possible if the polymer chain. has asystem of conjugated (altemate) double bonds. e.g. polyacetylene, polyparaphenylene, etc. have the system of conjugated double bonds throughout the chain. H H H H H H H | od 1G 1h NONE NF NF NOE NF NF Trans polyacetyiene | | I | H H H H | | H H Such conjugated double bonds have c-bond electrons localized but x-bond electrons ate not as strongly localized as the -bond electrons The conjugated ‘system. of bonds throughout the polymer chain can have delocalization of electrons by resonance. But still the conductivity of polyacetylene is found of the order of a semiconductor. State the applications of conducting polymers. Ans.: Conducting Polymers Polymeric materials are synthesized possessing electrical conductivities on par with metallic conductors. These polymers are called conducting polymers. Conductivities as high as 1.5 x 10’ ohm m” have been achieved in these materials. The phenomenon of conductivity is observed in a number of polymers such as polyacetylene, polyparaphenylene, polyprrole, polythiophene and polyaniline which have been doped with appropriate impurities. These polymers may be made either n-type (i.e., free electron dominant) or p-type (i.e., holes dominant) depending on the dopant. (i) n-doping : Polymer + M = (Polymer) + M™ where M = Na, Li ete. (ii) p-doping : Polymer + X = (Polymer) + X- where X = Io, Bry etc.84| Vidyalankar : F.E. - Chemistry | High purity polymers have electron band structures characteristics of electrical insulators. The dopant atoms leads to formation of new energy bands that overlap the valence and conduction bands of the intrinsic polymer, thereby giving rise to a partially filled conduction or valence band and the production at room temperature of a high concentration of free electrons or holes. During synthesis orientation of polymer chains, either mechanically or magnetically, results in a highly anisotropic material having a maximum conductivity along the direction of orientation. The conducting polymers have low densities, are highly flexible and are easy to produce. Applications : 1. In wiring in aircrafts and aerospace components. 2. In electronic devices such as transistors and diodes and in telecommunication systems. 3. In antistatic coating for clothing. 4, In electromagnetic. screening materials. 5. In photovoltaic devices. 5.9 GRADED QUESTIONS 1. What is polymerisation? What are the conditions for polymerization? 2. What is polymerization? Explain condensation polymerization with the help of an 21. example. Differentiate between Addition polymerisation and Condensation polymerisation. Describe a moulding method suitable for thermoplastic resins. [M-16] Thermosetting polymers cannot be reshaped and reused. Give reasons. IM-16] Distinguish between thermoplastic and thermosetting polymers. [D-15,16,17,18,19; M-17] With reference to polymers explain Glass transition temperature. [M-14] What is Glass transition temperature? [m-19] What is glass transition temperature? State the factors affecting it. [M-16,18] Explain the term “glass transition temperature”. What is its significance?! [M-16] . What is glass transition temperature? Write its significance [D-18] Discuss the effect of temperature on polymers. [M-19] Explain effect of heat on polymers and factors affecting it. [M-13] Explain the cause of electrical conductivity of doped conducting polymers. . Write short notes on : Conducting polymers. [0-17] Define conducting polymer. Explain how polymers are made conductors with suitable examples. [D-13] What are the various methods used for fabrication of plastic? Explain the compression moulding? . What is meant by fabrication of plastic? Explain in details the injection moulding method. [D-15] . What is fabrication of plastic? Explain injection moulding process with a neat diagram. [D-18] Name the methods for Fabrication of Plastics. With the help of labeled diagram describe Transfer moulding and Injection moulding. What are the advantages of transfer moulding?8 31. 32, 35. Module 5: Polymers | 85 Define moulding and discuss the Injection moulding method of fabrication of plastic. [D-13, 14; M-18] Define Fabrication. Explain Compression moulding with labelled diagram. [M-15] What is moulding? Explain with the help of a neat diagram Extrusion moulding of an insulated cable. [M-14] What is the function of plasticizer in the compounding of plastic? Give two examples. [M-15] What is compounding of plastic? Explain the role played by various constituents used during manufacturing of plastic. [M-19] . What are the moulding constituents of plastic? 28, Why plasticizers are added during moulding? Explain the following additives used for compounding of plastics: (i) Plasticizers, (ii) Resins, (ii) Catalysts [D-17; M-18] Explain the functions of the following constituents in the compounding of plasties. Give proper examples. (Any two) [0-15] (i) Fillers (i) Plasticizers (ji) Lubricants, (iv) Stabilizer What is compounding of plastics? Discuss the below mentioned constituents with appropriate examples: () Fillers, (ji) Pasticizers. [D-19] Give the preparation, properties and uses off : (i) PMMA [D-13,14,16,19; M-15] (ii) Kevlar [D-14,17,18,19; M-15,18] Discuss any two the following : [D-14] (i), Glass transition temperature. [D-19] (ii) Conducting polymers. Define the terms, () Monomer (ii), Polymer (ii) Degree of polymerization (iv) Co-polymerisation A polymer consists of 9 polymer chains as given below: [D-19] No. of polymer (N1) : 1 3 2 4. 2 Mol. Wt. of each polymer: 200 100. 300. 500 400 Calculate the number-average molecular weight of the polymer. [Ans.: M, = 266.67] goaqoa