INTRODUCTION:A polymer is a chemical compound or mixture of compounds consisting of repeating structural units created through a process of polymerization.

The term derives from the ancient Greek word (polus, meaning "many, much") and (meros, meaning "parts"), and refers to a molecule whose structure is composed of multiple repeating units, from which originates a characteristic of high relative molecular mass and attendant properties. The units composing polymers derive, actually or conceptually, from molecules of low relative molecular mass. The term was coined in 1833 by jons Jacob Berzelius, though with a definition distinct from the modern IUPAC definition. Historically, products arising from the linkage of repeating units by covalent chemical bonds have been the primary focus of polymer science; emerging important areas of the science now focus on non-covalent links.

Polymerisation :In polymer chemistry, polymerization is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or threedimensional networks.Polymerization process takes place in three distinct steps: 1. Chain initiation, usually by means of an initiator which starts the chemical process. Typical initiators include any organic compound with a labile group: e.g. azo (-N=N-), disulfide (-S-S-), or peroxide (-O-O-). Two examples are benzoyl peroxide and AIBN. 2. Chain propagation 3. Chain termination, which occurs either by combination or by dispropertionation.Termination, in radical polymerization, is when the free radicals combine and is the end of the polymerization process. Polymerization that is not sufficiently moderated and proceeds at a fast rate can be very hazardous. This phenomenon is known as hazardous polymerization and can cause fires and explosions.

Natural and Synthetic polymers :Natural polymeric materials such as shellac, amber, wool, silk and

natural rubber have been used for centuries. A variety of other natural polymers exist, such as cellulose, which is the main constituent of wood and paper. The list of synthetic polymers includes synthetic rubber, bakelite, neoprene, nylon, PVC, polystyrene, polyethelene, polypropylene, polyacrylonitrile, PVB, silicone, and many more.

HOMOPOLYMER AND CO-POLYMER :In general, polymers such as PVC are referred to as "homopolymers," as they consist of repeated long chains or structures of the same monomer unit, whereas polymers that consist of more than one molecule are referred to as copolymers (or co-polymers)..

Homopolymers

Copolymers

MONOMER ARRANGEMENT IN COPOLYMER :-

STEP GROWTH OR CHAIN GROWTH POLYMERIZATION:- Step-growth polymerization refers to a type

of polymerization mechanism in which bi-functional or multifunctional monomers react to form first dimers, then trimers, longer oligomers and eventually long chain polymers. Many naturally occurring and some synthetic polymers are produced by step-growth polymerization, e.g. polyesters, polyamides, polyurethanes, etc. Due to the nature of the polymerization mechanism, a high extent of reaction is

required to achieve high molecular weight. The easiest way to visualize the mechanism of a step-growth polymerization is a group of people reaching out to hold their hands to form a human chain each person has two hands (= reactive sites). There also is the possibility to have more than two reactive sites on a monomer: In this case branched polymers are produced.

A generic representation of a step-growth polymerization. (Single white dots represent monomers and black chains represent oligomers and polymers.

STEP GROWTH AND CONDENSATION POLYMERIZATION :- "Step growth polymerisation"

and condensation polymerization are two different concepts, not always identical. In fact polyurethane polymerizes with addition polymerization (because its polymerization produces no small molecules), but its reaction mechanism corresponds to a step-growth polymerization.

Chain growth polymerization :- Chain growth polymerization is

a polymerization technique where unsaturated monomer molecules add on to a growing polymer chain one at a time. The distinction between "step-growth polymerization" and "chain-growth polymerization" was introduced by Paul Flory in 1953, and refers to the reaction mechanisms, respectively:

by functional groups (step-growth polymerization) by free-radical or ion (chain-growth polymerization)

DIFFERENCES BETWEEN STEP GROWTH AND CHAIN GROWTH POLMERIZATION:Step-growth polymerization Chain-growth polymerization
Growth by addition of monomer only at one end of chain Some monomer remains even at long reaction times Different steps operate at different stages of mechanism (i.e. Initiation, propagation and termination) Molar mass of backbone chain increases rapidly at early stage and remains approximately the same throughout the polymerization

Growth throughout matrix

Rapid loss of monomer early in the reaction

Similar steps repeated throughout reaction process

Average molecular weight increases slowly at low conversion and high extents of reaction are required to obtain high chain length

Ends remain active (no termination)

Chains not active after termination

No initiator necessary

Initiator required

CLASSES OF STEP GROWTH POLYMERS:

Polyester has high melting point Tm, good mechanical properties to about 175 C, good resistance to solvent and chemicals. It can exist as fibers and films. The former is used in garments, felts, tire cords, etc. The latter appears in magnetic recording tape and high grade films. Polyamide (nylon) has good balance of properties: high strength, good elasticity and abrasion resistance, good toughness, favorable solvent resistance. The applications of polyamide include: rope, belting, fiber cloths, thread, substitute for metal in bearings, jackets on electrical wire.

Polyurethane can exist as elastomers with good abrasion resistance, hardness, good resistance to grease and good elasticity, as fibers with excellent rebound, as coatings with good resistance to solvent attack and abrasion and as foams with good strength, good rebound and high impact strength. Polyurea fair resistance to greases, oils, and solvents. It can be used in truck bed liners, bridge coating, caulk and decorative designs. Polysiloxane are available in a wide range of physical statesfrom liquids to greases, waxes, resins, and rubbers. Uses of this material are as antifoam and release agents, gaskets, seals, cable and wire insulation, hot liquids and gas conduits, etc. Polycarbonates are transparent, self-extinguishing materials. They possess properties like crystalline thermoplasticity, high impact strength, good thermal and oxidative stability. They can be used in machinery, auto-industry, and medical applications. For example, the cockpit canopy of F-22 Raptor is made of high optical quality polycarbonate. Polysulfides have outstanding oil and solvent resistance, good gas impermeability, good resistance to aging and ozone. However, it smells bad, and it shows low tensile strength as well as poor heat resistance. It can be used in gasoline hoses, gaskets and places that require solvent resistance and gas resistance. Polyether shows good thermoplastic behavior, water solubility, generally good mechanical properties, moderate strength and stiffness. It is applied in sizing for cotton and synthetic fibers, stabilizers for adhesives, binders, and film formers in pharmaceuticals.

Phenol formaldehyde resin (Bakelite) have good heat resistance, dimensional stability as well as good resistance to most solvents. It also shows good dielectric properties. This material is typically used in molding applications, electrical, radio televisions and automotive parts where their good dielectric properties are of use. Some other uses include: impregnating paper, varnishes, decorative laminates for wall coverings. ADDITION AND CONDENSATION POLYMERS:- An is a polymer which is formed by an addition reaction, where many monomer

bond together via rearrangement of bonds without the loss of any atom or molecule. This is in contrast to a condensation polymer which is formed by a condensation reaction where a molecule, usually water, is lost during the formation.

General chemical structure of one type of condensation polymer

SOME COMMONLY USED ADDITION POLYMERS :1.LOW- DENSITY POLYETHYLENE (LDPE) :Low-density polyethylene (LDPE) is a thermoplastic made from the monomer ethylene. It was the first grade of polyethylene, produced in 1933 by Imperial Chemical Industries (ICI) using a high pressure process via free radical polymerization. It is prepared in presence of traces of oxygen, in presence of peroxide, at 1000-2000 atmospheric pressure and at 350-470 k.

Properties:- LDPE is defined by a density range of 0.9100.940 g/cm3. It

is not reactive at room temperatures, except by strong oxidizing agents, and some solvents cause swelling. It can withstand temperatures of 80 C continuously and 95 C for a short time. Made in translucent or opaque variations, it is quite flexible, and tough but breakable. LDPE has more branching (on about 2% of the carbon atoms) than HDPE, so its intermolecular forces (instantaneous-dipole induced-dipole attraction) are weaker, its tensile strength is lower, and its resilience is higher. Also, since its molecules are less tightly packed and less crystalline because of the side branches, its density is lower. LDPE contains the chemical elements carbon and hydrogen.

Chemical resistance:1.Excellent resistance (no attack) to dilute and concentrated acids, alcohols, bases and esters. 2.Good resistance (minor attack) to aldehydes, ketones and vegetable oils. 3.Limited resistance (moderate attack suitable for short-term use only) to aliphatic and aromatic hydrocarbons, mineral oils, and oxidizing agents. 4.Poor resistance, and not recommended for use with halogenated hydrocarbon.

Applications:- LDPE is widely used for manufacturing various

containers, dispensing bottles, wash bottles, tubing, plastic bags for computer components, and various molded laboratory equipment. Its most common use is in plastic bags. Other products made from it include:

Trays and general purpose containers Corrosion-resistant work surfaces Parts that need to be weldable and machinable Parts that require flexibility, for which it serves very well Very soft and pliable parts such as snap-on lids Juice and milk cartons are made of liquid packaging board, a laminate of paperboard and LDPE (as the water-proof inner and outer layer), and often with of a layer of aluminum foil (thus becoming aseptic packaging). Parts of computer hardware, such as hard disk drives, screen cards, and optical disc drives Playground slides Plastic wraps

High-density polyethylene (HDPE):High-density polyethylene (HDPE) or polyethylene high-density (PEHD) is polyethylene thermoplastic made from petroleum. It takes 1.75 kilograms of petroleum (in terms of energy and raw materials) to make one kilogram of HDPE. It is prepared at 333-343 K and at 6-7 atmospheric pressure in presence of Ziegler-Natta catalyst.

APPLICATIONS :- LDPE is resistant to many different solvents and has

a wide variety of applications, including:- Arena Board (puck board), Backpacking frames, Ballistic plates,Bottle caps, Chemical resistant piping

systems, Food storage containers, Bottles, suitable for re-use, Fuel tanks for vehicles,Laundry detergent bottles,Milk jugs,Corrosion protection for steel pipelines, Folding chairs and tables, Geothermal heat transfer piping systems, Floorball Blades,Hard Hats, Meter & Valve Boxes,Natural gas distribution pipe systems,Plastic bags, Plastic lumber, Plastic surgery (skeletal and facial reconstruction),Telecom ducts, Water pipes, for domestic water supply and agricultural processes.

2.Polypropylene:- Polypropylene (PP), also known as polypropene,

is a thermoplastic polymer used in a wide variety of applications including packaging and labeling, textiles (e.g., ropes, thermal underwear and carpets), stationery, plastic parts and reusable containers of various types, laboratory equipment,loudspeakers, automotive components, and polymer banknotes. An addition polymer made from the monomer propylene, it is rugged and unusually resistant to many chemical solvents, bases and acids.

FIGURE OF POLYPROPENE

/plistarin/) is an aromatic polymer made from the monomer styrene, a liquid petrochemical. Polystyrene is one of the most widely used plastics, the scale of its production being several billion kilograms per year.It is a colorless solid that is used, for example, in disposable cutlery, plastic models, CD and DVD cases, and smoke detector housings. Products made from foamed polystyrene are ubiquitous, for example packing materials, insulation, and foam drink cups. Its very slow biodegradation is a focus of controversy, and it is often abundant as a form of litter in the outdoor environment, particularly along shores and waterways especially in its low density cellular form.

3.Polystyrene :- Polystyrene (PS) (

FIGURE OF POLYSTYRENE

FIGURE SHOWING POLYMERIZATION OF STYRENE

4.Polyacrylonitrile (PAN):- Polyacrylonitrile (PAN) is a synthetic,

semicrystalline organic polymer resin, with the linear formula (C3H3N)n. Though it is thermoplastic, it does not melt under normal conditions. It degrades before melting. It melts above 300 y if the heating rates are 50 degrees per minute or above. Almost all polyacrylonitrile resins are copolymers made from mixtures of monomers with acrylonitrile as the main component. It is a versatile polymer used civil and military aircraft primary and secondary structures, missiles, solid propellant rocket motors, pressure vessels, fishing rods,tennis rackets, badminton rackets & high-tech bicycles.

FIGURE OF POLYACRLONITRILE

5.Polyvinyl chloride:-

Polyvinyl chloride, commonly abbreviated PVC, is the third-most widely produced plastic, after polyethylene and polypropylene. PVC is used in construction because it is cheaper and stronger than more traditional alternatives such as copper or ductile iron. It can be made softer and more flexible by the addition of plasticizers. In this form, it is used in clothing, electrical cable insulation, inflatable products and many applications in which it replaces rubber. Pure polyvinyl chloride without any plasticizer is a white, brittle solid. It is insoluble in alcohol, but slightly soluble in tetrahydrofuran.

FIGURE OF POLYVINYL CHLORIDE

6.POLYMETHYLMETHACRYLATE (PMMA) :- Its monomer is

methylmethacrylate. It is commercially known as plexi glass or Perspex. It has excellent light transmission properties even better than glass. It is used in the preparation of transparent domes, lenses, light covers, aircraft window and artificial jewellery, etc.

FIGURE OF POLYMETHYLMETHACRYLATE(PMMA)

7.POLYTETRAFLUOROETHYLENE(PTFE) :Polytetrafluoroethylene (PTFE) is a synthetic fluoropolymer of tetrafluoroethylene that finds numerous applications. The best known brand name of PTFE is Teflon by DuPont Co. PTFE is a fluorocarbon solid, as it is a high-molecular-weight compound consisting wholly of carbon and fluorine. PTFE is hydrophobic: neither water nor water-containing substances wet PTFE, as fluorocarbons demonstrate mitigated London dispersion forces due to the high electronegativity of fluorine. PTFE has one of the lowest coefficients of friction against any solid. PTFE is used as a non-stick coating for pans and other cookware. It is very non-reactive, partly because of the strength of carbonfluorine bonds, and so it is often used in containers and pipework for reactive and corrosive chemicals. Where used as a lubricant, PTFE reduces friction, wear, and energy consumption of machinery.

FIGURE OF POLYTETYRAFLUOROETHYLENE (PTFE)

8.Polychlorotrifluoroethylene (PCTFE or PTFCE) :Polychlorotrifluoroethylene (PCTFE or PTFCE) is a thermoplastic chlorofluoropolymer with the molecular formula (CF2CClF)n, where n is the number of monomer units in the polymer molecule. It is similar to polytetrafluoroethylene (PTFE), except that it is a homopolymer of the monomer chlorotrifluoroethylene (CTFE) instead of tetrafluoroethylene. It has the lowest water vapor transmission rate of any plastic.

FIGURE OF POLYMONOCHLOROTRIFLUOROETHYLENE

SOME COMMONLY USED CONDENSATION POLYMERS :1.Nylon 6 (polycaprolactam, polyamide 6, PA6) :Nylon 6 is a a polymer developed by Paul Schlack at IG Farben to reproduce the properties of nylon 6,6 without violating the patent on its production. Unlike most other nylons, nylon 6 is not a condensation polymer, but instead is formed by ring-opening polymerization. This makes it a special case in the comparison between condensation and addition polymers. Its competition with nylon 6,6 and the example it set have also

shaped the economics of the synthetic fiberindustry. It was given the trademark Perlon in 1952. It is a semicrystalline polyamide. Nylon 6 fibres are tough, possessing high tensile strength, as well as elasticity and lustre. They are wrinkle-proof and highly resistant to abrasion and chemicals such as acids and alkalis. The fibres can absorb up to 2.4% of water, although this lowers tensile strength. Nylon 6 is used as thread in bristles for toothbrushes, surgical sutures, and strings for acoustic and classical musical instruments, including guitars, sitars, violins, violas, and cellos. It is also used in the manufacture of a large variety of threads, ropes, filaments, nets, and tire cords, as well as hosiery and knitted garments. It can also be used in gun frames.

FIGURE OF CAPROLACTUM- MONOMER OF NYLON-6

FIGURE OF POLYMERIZATION OF CAPROLACTUM

2.NYLON-6,6:-

Nylon 6,6 is made of hexamethylenediamine and adipic acid, which give nylon 6,6 a total of 12 carbon atoms in each repeating unit.

FIGURE OF ADIPIC ACID

FIGURE OF HEXAMETHYLENEDIAMINE Hexamethylene diamine and adipic acid are combined with water in a reactor. This produces nylon salt. The nylon salt is then sent to an evaporator where excess water is removed.The nylon salt goes into a reaction vessel where a continuous polymerization process takes place. This chemical process makes molten nylon 6,6.The molten nylon 6,6 undergoes a spinning process, where the nylon 6,6 is extruded and sent through a spinneret, which is a small metal plate with fine holes. The nylon is then air-cooled to form filaments.Nylon's chemical formula is nHOOC(CH2)4-COOH+n H2N-(CH2)6-NH2---->[-OC-( CH2)4-CO-NH-(CH2)6-NH-] n+2nH2O and the part -CO-NH- will stick together becoming Nylon 6,6. USES:- Carpet fiber, apparel, airbags, tyre cords, climbimg ropes,Conveyor Belts, Hoses, etc. /beklat/ BAY-k-lyt), or polyoxybenzylmethylenglycolanhydride, is an early plastic. It is a thermosetting phenol formaldehyde resin, formed from an elimination reaction of phenol with formaldehyde. It was developed by Belgian-born chemist Leo Baekeland in New York in 1907.

3.BAKELITE :- Bakelite (

One of the first plastics made from synthetic components, Bakelite was used for its electrical nonconductivity and heat-resistant properties in electrical insulators, radio and telephone casings, and such diverse products as kitchenware, jewelry, pipe stems, and children's toys.

FIGURE OF BAKELITE

4.Melamine resin or melamine formaldehyde :Melamine resin or melamine formaldehyde (also shortened to melamine) is a hard, thermosetting plastic material made from melamine and formaldehyde by polymerization. In its butylated form, it is dissolved in nbutanol and xylene. It is then used to cross-link with alkyd, epoxy, acrylic, andpolyester resins, used in surface coatings. It is used in making unbreakable crockery.

FIGURE OF MELAMINE FORMALDEHYDE RESIN

RUBBERS:- Natural rubber is obtained from latex of rubber

plant.Chemically it is 2-Methylbut-1,4-diene and commonly known as isoprene. Natural rubber is vulcanized to improve its properties.

VULCANIZATION:- Vulcanization or vulcanisation is a chemical

process for converting rubber or related polymers into more durable materials via the addition of sulfur or other equivalent "curatives" or "accelerators". These additives modify the polymer by forming crosslinks (bridges) between individual polymer chains. Vulcanized materials are less sticky and have superior mechanical properties. A vast array of products are made with vulcanized rubber including tires, shoe soles, hoses, etc. The process is named after Vulcan, Roman god of fire. Hard vulcanized rubber is sometimes sold under the brand names ebonite or vulcanite, and is used to make hard articles such as bowling balls and saxophone mouth pieces.

NATURAL VS VULCANIZED RUBBER :-Uncured natural

rubber is sticky, deforms easily when warm, and is brittle when cold. In this state, it is a poor material when a high level of elasticity is required. The reason for inelastic deformation of un-vulcanized rubber can be found in its chemical structure: rubber is composed of long polymer chains. These chains can move independently relative to each other, which lets the material change shape. Crosslinking introduced by vulcanization prevents

the polymer chains from moving independently. As a result, when stress is applied the vulcanized rubber deforms, but upon release of the stress, the article reverts to its original shape.

The main polymers subjected to vulcanization are polyisoprene (natural rubber) and styrene-butadiene rubber (SBR), which are used for most passenger tires.The reactive sites"cure sites"are allylic hydrogen atoms. These C-H bonds are adjacent to carbon-carbon double bonds. During vulcanization, some of these C-H bonds are replaced by chains of sulphur atoms that link with a cure site of another polymer chain. These bridges contain between one and eight atoms. The number of sulphur atoms in the crosslink strongly influences the physical properties of the final rubber article. Short crosslinks give the rubber better heat resistance. Crosslinks with higher number of sulphur atoms give the rubber good dynamic properties but with lesser heat resistance. Dynamic properties are important for flexing movements of the rubber article, e.g., the movement of a side-wall of a running tire.

SOME COMMERCIALLY IMPORTANT RUBBERS :1.NEOPRENE :- Neoprene or polychloroprene is a family of synthetic

rubbers that are produced by polymerization of chloroprene. Neoprene exhibits good chemical stability, and maintains flexibility over a wide temperature range. It is used in a wide variety of applications, such as laptop sleeves,orthopedic braces (wrist, knee, etc.),conveyor belts in coal mines.

FIGURE REPRESENTING NEOPRENE

FIGURE REPRESENTING FORMATION OF NEOPRENE

2.STYRENE BUTADIENE RUBBER :- Styrene-butadiene or styrenebutadiene rubber (SBR) describe families of synthetic rubbers derived from styrene and butadiene. These materials have good abrasion resistance and good aging stability when protected by additives.The styrene/butadiene ratio influences the properties of the polymer: with high styrene content, the rubbers are harder and less rubbery.

FIGURE REPRESENTING STYRENE-BUTADIENE RUBBER The elastomer is used widely in pneumatic tires, shoe heels and soles, gaskets and even chewing gum. It is a commodity material which competes with natural rubber. It is also used in building applications, as a sealing and binding agent. In the latter application, it offers better durability, reduced shrinkage and increased flexibility, as well as being resistant to emulsification in damp conditions.

3.Buna-N :- Nitrile rubber, also known as Buna-N, Perbunan, or NBR,

is a synthetic rubber copolymer of acrylonitrile (ACN) and butadiene. Trade names include Nipol, Krynac and Europrene.

Nitrile butadiene rubber (NBR) is a family of unsaturated copolymers of 2propenenitrile and various butadiene monomers (1,2-butadiene and 1,3butadiene). Although its physical and chemical properties vary depending on the polymers composition of nitrile, this form of synthetic rubber is generally resistant to oil, fuel, and other chemicals (the more nitrile within the polymer, the higher the resistance to oils but the lower the flexibility of the material). Nitrile butadiene is used to create moulded goods, footwear, adhesives, sealants, sponges, expanded foams, and floor mats. Its resilience makes NBR a useful material for disposable lab, cleaning, and examination gloves. Nitrile rubber is more resistant than natural rubber to oils and acids, but has inferior strength and flexibility. Nitrile gloves are nonetheless three times more puncture-resistant than natural rubber gloves.

BIODEGRADABLE SYNTHETIC POLYMERS :Poly(3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV) :PHBV is a polyhydroxyalkanoate-type polymer. It is biodegradable, non toxic, biocompatible plastic produced naturally by bacteria and a good alternative for many non-biodegradable synthetic polymers. It is a thermoplastic linear aliphatic polyester.

FIGURE OF PHBV PHBV is a co-polymer of 3-hydroxybutanoic acid and 3-hydroxypentanoic acid. PHBV find its applications in controlled release of drugs, medical implants and repairs, specialty packaging, orthopedic devices and manufacturing bottles for consumer goods.

It has very good scope in tissue engineering. The favoring properties are biocompatibility and in vivo degradation into its monomers, which are normal in the blood.

DEGRADATION :When disposed, PHBV degrades into carbon dioxide and water. PHBV undergo bacterial degradation. PHBV, just like fats to human, is an energy source to microorganisms. Enzymes produced by them degrade it and are consumed. PHBV has a low thermal stability and the cleavage occurs at the ester bond by elimination reaction.

DRAWBACKS:- Low thermal stability, expensive, brittle, processing

difficulty and primitive mechanical properties.