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PLASTICS AND POLYMERS

Polymers and Polymerization


Polymers are compounds which consist of very large molecules formed by repeated joining of many small molecules The repeating unit in the molecule is called monomer.

Polymers consisting of a single type of monomer molecules are known as homopolymers. The polymers obtained from monomers of different types are called copolymers.

Homopolymer
Example: Polythene, nylone-6, Polystyrene, Polyvinyl chloride (PVC)

-A-A-A-A-A-A-A-A-

Copolymer
Example: Nylone-6.6, Styrene-butadiene rubber (SBR), Buna-S, Bakelite.

-A-B-A-B-A-B-A-B-A-B-

1 2 3 4

Based upon Natural and synthetic polymers source Based upon Addition and condensation polymers synthesis Based upon Inorganic and organic polymers elements Based upon molecular forces. Plastic: Intermolecular forces of attraction are intermediate between those of elastomers and fibers. Elastomers: Chains are held together by weak forces Fibers: Held together by strong inter molecular forces.

Elastomer Fibre

Plastic

35.1 Introduction (SB p.151)

Naturally Occurring Polymers and Synthetic Polymers

The most important naturally occurring polymers are: Proteins Polysaccharides (e.g. cellulose, starch) Nucleic acids (e.g. DNA, RNA) Rubber

Cotton fiber is mostly cellulose, and cellulose is made of chains of the sugar, glucose linked together a certain way.

Elastomers include all those polymers, whose chains are held together by weak forces and hence can be stretched by pulling and on relieving the stress, can be made to regain their original shape. Eg: Rubber

Natural Rubber A hydrocarbon C5H8 isoprene-(2-methyl-1,3-butadiene) which is the repeating unit in rubber. Rubber contains 16000-20000 units in one string.

2003 John Wiley and Sons Publishers

Rubber is a natural elastomer

Rubber forms by addition polymerization of isoprene

Vulcanization It is the process of heating natural rubber with sulphur (3-5%), H2S, benzoyl chloride to a temperature range 110-140oC. Merits of Vulcanization 1.It helps in preventing the slippage of chains on application of stress. 2.It makes rubber less sensitive to temperature changes. 3.It increases elasticity, tensile strength and extensibility. 4.It increases the resistance of rubber to oxidation, abrasion, wear and tear, water and organic solvents. 5.Rubber becomes a better electrical insulator as a result of vulcanization

2003 John Wiley and Sons Publishers

Vulcanized Rubber Untreated natural rubber When you heat rubber with
becomes soft and sticky when it is warm

sulfur it becomes modified to allow it to stay elastic when it is warm

Applications of Rubber

1. For making rubber bands, golf balls, mechanical rubber goods, rubber gaskets for sealing equipments like pressure cooker, refrigerators doors etc. 2. For making automobile and aeroplane tyres due to its abrasion resistance. 3. In telephone receivers, battery cases, electrical switch board panels etc. 4. Due to its remarkable resistance to electricity used for insulating coating on wires and cables. 5. In medicine, rubber is used for making heart valves, transfusion tubings, padding for plastic surgery etc. 6. It finds uses as an eraser and adhesive too.

Synthetic Rubber These are man made, rubber like polymer


Eg: Buna-S, Thiokol, Buna-N

Name
1 2 3 4 5 6
Buna-S Buna-N

Uses
Manufacture of motor tyres, gaskets, wire & cable insulation. Conveyer belts, high components, hoses automobile parts. floor tiles, altitude air craft printing rollers,

Neoprene Butyl Rubber Thiokol Silicon rubber

Wire insulations, cable covering for conveyer belts and chemical apparatus, sponges etc. Cycle and automobiles parts, tank linings Hoses, gaskets and covering for cables. Artificial heart valves, transfusion tubes and padding for plastic surgery, in lubricants, paints and protective coatings, shoes.

Plastics are found everywhere


Except for our food, air, and water almost every ordinary thing that we come in contact with contains some sort of plastic in, on, or around it.

Plastics come in an amazing variety of colors, shapes, types, and textures Plastics have found applications in nearly everything that we use

PLASTICS
It is a polymer which can be moulded into various shapes, can be recycled, remoulded and reused.

A plastic is a material which shows the property of plasticity ie, capacity to change to different forms under pressure. Plastics may be defined as organic material of high molecular mass, which can be moulded into any desired shape, by subjecting to suitable heat and pressure conditions in presence of a catalysts.

TYPES OF PLASTICS Plastics are of two types: Thermoplastics Thermosetting plastics

THERMOPLASTICS
Plastics which can be moulded on heating and used again. Example: polythene, PVC.

The arrangement of particles (monomers) in thermoplastics is linear and these can be recycled.

POLYTHENE
Monomer: ethene Use: for making polythene bags, toys and combs.

Monomer: vinyl chloride Use: for making pipes, toys and combs.

PVC (POLY VINYL CHLORIDE)

Plastic which once set cannot be moulded on heating. Example: Bakelite and melamine.

THERMOSETTING PLASTIC

The arrangement of particles (monomers) in thermosetting plastic is cross linked and these cannot be recycled.

BAKELITE
It is a poor conductor of heat and electricity. Use: for making electrical switches, handles of various utensils.

MELAMINE
It is resistant to fire and can tolerate heat. Use: for making floor tiles, kitchen ware and fabrics which resist fire.

Thermoplastics

Thermosetting Plastic
They have formed by condensation polymerization and usually have three dimensional extensive cross linking between the polymer chains.

They have formed by addition polymerization and usually have linear structure

2 3

They are soft, weak and less They are more hard, strong brittle and brittle and are soluble in organic insoluble in organic solvents. solvents Can be remoulded, recast reshaped, and reused by application of suitable pressure and temperature. Cannot be remoulded or reshaped. Once set, it cannot be recast by any means.

4 5

On heating they soften and On heating, do not soften, rather they become fluid but on cooling become hard and infusible, prolonged become hard. heating make them burn. Eg. Cellulose acetate, PVC, Bakelite, polyester, terylene, resins, Polythene, Polypropylene, Teflon urea-formaldehyde polymer ect. etc.

Nylon 6,6
It is formed by the condensation polymerisation of adipic acid and hexamethylene diamine. It is a polyamide polymer. n HOOC-(CH2)4COOH Adipic acid

n H2N-(CH2)6-NH2
Hexamethylene diamine

O -[-OC-(CH -C-NH-(CH n H2O 2)4 2)6+ NH-]n Nulon-6,6 is stronger than natural fibres. They are elastic, light weight, very strong and flexible, inert to chemicals and biological agents and are used in making fabrics, carpets, tyre cords, ropes etc .

Nylon 6
It is manufactured by prolonged heating of caprolactum at 260270oC. It is another polyamide polymer. H N CH2 CH2 C H2 C H2 C=O CH2
260-270oC

O -[ -C-NH-(CH 2)5-]n-

Caprolactum

Nylon 6

Terylene or Dacron Condensation polymerization of terephthalic acid and ethylene glycol, in presence of a weak base results in the formation of the most important polyester fabric named Terylene.
HOOC
Teraphthalic acid

COOH

OH-CH2-CH2-OH
Ethylene Glycol

-[-OC-C6H4-CO-O-CH2-CH2-O-]n-

Orlon

Polymerization of acrilonitrile (vinylcyanide) in presence of FeSO4 and H2O2, gives orlon. It is water resistant quick drying, can be woven or knitted, can be blend with wool, used in making cloths, carpets, blankets etc.
n CH2=CHCN
Polymerization

Fe2SO4/H2O2

-[CH2-CH-]CN

Fibres are thread like bits of materials characterized by great tensile strength in the direction of the fibre. Cloths are making from fibres. Types of Fibre.. 1.Natural fibre, obtained from natural sources like cotton, jute, wool and silk. 2.Semi synthetic fibres, obtained from natural sources eg: cellulose, which is heated with special reagents to bring it to solution or dispersed state and then turned into filaments Eg: Rayons. 3.Synthetic fibres, obtained by addition or condensation polymerization. Eg: Nylon, terylene, orlon etc.

N O M M CO

D N A S C I T S A L P

R I E TH

S U

S E

A polymer made form just one monomer is polyethylene. It is the most common plastic you see. It is used for bottles, buckets, jugs, containers, toys, even synthetic lumber, and many other things.

High Density Polyethene(HDPE) is used in making Detergent bottles, milk jugs, and molded plastic cases.

low density polyethylene (LDPE). It is made by causing the long chains of ethylene to branch. That way they cannot lie next each other, which reduces the density and strength of the polyethylene. This makes the plastic lighter and more flexible.

Low density polyethylene is used to make plastic bags, plastic wrap, and squeeze bottles, plus many other things.

POLY PROPYLENE
It serves double duty, both as a plasticand as a fiber. As a plastic it's used to make things like dishwasher-safe food containers. It can do this because it doesn't melt below 160oC, or 320oF
Asa fibre, polypropylene is used to make indoor-outdoor carpeting, the kind that you always find around swimming pools and miniature golf courses. It works well for outdoor carpet because it is easy to make colored polypropylene, and because polypropylene doesn't absorb water, like nylone does.

Polypropylene can be made from the monomer propylene by Ziegler Nutta polymerisation

Polystyrene
Polystyrene is an inexpensive and hard plastic

The outside housing of the computer you are using now is probably made of polystyrene. Model cars and airplanes are made from polystyrene, and it also is made in the form of foam packaging and insulation . Clear plastic drinking cups are made of polystyrene. So are a lot of the molded parts on the inside of your car, like the radio knobs. Polystyrene is also used in toys, and the housings of things like hairdryers, computers, and kitchen appliances

POLYSTYRENE Polystyrene is a rigid, brittle, inexpensive plastic that has been used to makeplastic model kits and similar knick-knacks. Polystyrene is produced by free radical polymerisation , from the monomer styrene.

Polystyrene is also a component of a type of hard rubber called poly(styrene-butadienestyrene) , or SBS rubber. SBS rubber is a thermoplastic elastomers.

NYLONE
The plastics industry was revolutionized in the 1930s with the announcement of Polyamide(PA), far better known by its trade name nylon. Nylon was the first purely synthetic fiber, introduced by DuPont coparation at the 1939 worlds fair in New York city.

Nylons still remain important plastics, and not just for use in fabrics. In its bulk form it is very wear resistant, particularly if oilimpregnated, and so is used to build gears,Plain bearings, valve seats, seals and because of good heat-resistance, increasingly for under-the-hood applications in cars, and other mechanical parts.

Tetramethylene dicarboxylic acid (adipic acid)

Hexamethylene diamine

methylene x 6 (hexa)

amine x 2 (di)

Nylon is actually a copolymer because is it made from two monomers. When these two monomers are in the same beaker, they combine and give off a molecule of water. This is called a dehydration reaction because we are taking away (de) water (hydra). (regarding odor: amines smell like fish or worse. Adipic acid is odorless )

NYLON 6
Another kind of nylon is nylon 6. It's a lot like nylon 6,6 except that it only has one kind of carbon chain, which is six atoms long.
It's made by a ring open polymerisation form the monomer caprolactam. Nylon 6 doesn't behave much differently from nylon 6,6. The only reason both are made is because DuPont patented nylon 6,6, so other companies had to invent nylon 6 in order to get in on the nylon business.

Polyester is another copolymer. It is made from equal amounts of two different monomers. Polyester is used to make bottles and fabrics.

Polyester is made from the two monomers, terephthalic acid (note: ph is silent) and ethylene glycol (car antifreeze). This makes a popular plastic called PETE, which is short for Polyethylene Terephthalate. The synthesis is also a dehydration reaction because water is given off. PE TE

O
H O

ESTER groups formed

Hence the name POLYESTER

POLY VENYL CHLORIDE (PVC) Another polymer, which is almost the same as polyethylene, is PolyVinyl Chloride or PVC. The difference is that every other hydrogen is replaced with a chlorine atom (green sphere).

PVC pipes are used in our homes and they are even handy for making a table or chair.

PVC is used inPlumbing pipes and


guttering, shower curtains, window frames, flooring.

PVC is also used as insulation around electric wires in the home and the automobile.

PVC is quite safe until it burns. When it burns, the chlorine in the PVC combine with the hydrogen atoms in the PVC to form hydrogen chloride gas (HCl). When this contacts water in lungs or mouth, it turns to hydrochloric acid (HCl(aq)).

(CH2CHCl)n + O2 CO2 + CO + HCl + H2O

POLY VENYL ACETATE PVA is used to make wood glues, as well as other adhesives. Paper and textiles often have coatings made of PVA and other ingredients to make them shiny.
It's made by free radical venylpolymerisation of the monomer vinyl acetate.

EPOXY RESINS

Epoxy resins make great adhesives, and are one of the few adhesives that can be used on metals. But they're also used for things like protective coatings, and as materials in things like electronic circuit boards and for patching holes in concrete pavement.

POLY ACRYLONITRILE (PAN)


Polyacrylonitrile is a vinylpolymer, and a derivative of the acrylate familyof polymers. It is made from the monomer acrylonitrile byfree radical vinylpolymerisation

Sweaters can also be made out of acrylics, like Poly acrylonitrile

Homopolymers of polyacrylonitrile have been used as fibers in hot gas filtration systems, outdoor awnings, sails for yachts, and even fiber reinforced concrete. But mostly copolymers containing polyacrylonitrile are used as fibers to make knitted clothing, like socks and sweaters, as well as outdoor products like tents and such.

Kevlar (poly paraphenylene terephthalamide) Kevlar is the registered trademark for a paraaramid synthetic fiber

Kevlar is synthesized in solution from the monomers 1,4-phenylene-diamine (paraphenylenediamine) and terephthaloyl chloride in a condensation reaction

Kevlar has many applications, ranging from bicycle tires and racing sails to body armor because of its high tensile strength-to-weight ratio; by this measure it is 5 times stronger than steel on an equal weight basis Kevlar is a well-known component of personal armor such as combat helmets, ballistic face masks, and ballistic vests. Other military uses include bulletproof facemasks

It is used as an inner lining for some bicycle tires to prevent punctures, and due to its excellent heat resistance

Synthetic rubber is any type of artificial elastomers, invariably a polymer. An elastomer is a material with the mechanical (or material) property that it can undergo much more elastic deformation under stress than most materials and still return to its previous size without permanent deformation. Synthetic rubber serves as a substitute for natural rubber in many cases, especially when improved material properties are required.

POLY CHLOROPRINE Polychloroprene is a synthetic rubber made from the monomer chloroprene
Polychloroprene is usually sold under the trade name Neoprene. It's especially resistant to oil.

SBR
Styrene-butadiene or styrene-butadiene rubber (SBR) is a synthetic rubber copolymer consisting of styrene and butadiene. It has good abrasion resistance and good aging stability when protected by additives, and is widely used in car tires, where it may be blended with natural 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. Latex (emulsion) SBR is extensively used in coated papers, being one of the most cost-effective resins to bind pigmented coatings. It is also used in building applications, as a sealing and binding agent behind renders as an alternative to PVA, but is more expensive

PMMA(POLY METHYLMETHACRYLATE PMMA, is a clear plastic used as a shatterproof replacement When it comes to making windows, PMMA has another advantage over glass. PMMA is more transparent than glass. When glass windows are made too thick, they become difficult to see through. But PMMA windows can be made as much as 13 inches (33 cm) thick, and they're still perfectly transparent. This makes PMMA a wonderful material for making large aquariums, whose windows must be thick in order to contain the high pressure millions of gallons of water

Acrylic "latex" paints often contain PMMA suspended in water

PMMA is also used in Contact lenses, glazing (best known in this form by its various trade names around the world; e.g., Perspex, Oroglas, Plexiglas), aglets, fluorescent light diffusers, rear light covers for vehicles. It forms the basis of artistic and commercial acrylic paints when suspended in water with the use of other agents. PMMA is avinyl polymer, made by free

radical vinyl polymerisation from the monomer methyl methacrylate.

Bakelite,
Bakelite or polyoxybenzylmethylenglycolanhydride, is an early plastic. It is thermosetting phenolformaldehyde resin, formed from an elimination reaction of phenol withformaldehyde. It was developed in 1907 by Belgianborn chemist Leo Baekeland. One of the first plastics made from synthetic components, Bakelite was used for its electrically nonconductivityand heat-resistant properties in electricalinsulators, radio and telephone casings, and such diverse products as kitchenware,jewelry, pipe stems, and childrens toys

POLY URETHANE
Poly urethane(PU) Poly urethane is used in Cushioning foams, thermal insulation foams, surface coatings, printing rollers (Currently 6th or 7th most commonly used plastic material, for instance the most commonly used plastic found in cars).

Melamine formaldehyde(MF) One of the aminoplasts, and used as a multi-colorable alternative to phenolics, for instance in moldings (e.g., break-resistance alternatives to ceramic cups, plates and bowls for children) and the decorated top surface layer of the paper laminates (e.g., Formica).

It is a thermosetting plastic, with the familiar trade name Bakelite, that can be molded by heat and pressure when mixed with a filler-like wood flour or can be cast in its unfilled liquid form or cast as foam (e.g., Oasis). Problems include the probability of moldings naturally being dark colors (red, green, brown), and as

POLYTETRAFLOUROETHYLENE

Polytetrafluoro ethylene (PTFE) Heat-resistant, lowfriction coatings, used in things like non-stick surfaces for frying pans, plumber's tape and water slides. It is more commonly known as Teflon.

UREA FORMALDEHYDE Urea formaldehyde (UF) One of the aminoplasts and used as a multi-colorable alternative to phenolics. Used as a wood adhesive (for plywood, chipboard, hardboard) and electrical switch housings.

POLY TETRA FLOURO ETHYLENE (PTFE)

Polytetrafluoroethylene is better known by the trade name Teflon. It's used to make non-stick cooking pans, and anything else that needs to be slippery or non-stick. PTFE is also used to treat carpets and fabrics to make them stain resistant. What's more, it's also very useful in medical applications. Because human bodies rarely reject it, it can be used for making artificial body parts. Polytetrafluoroethylene is made from the monomer tetrafluoroethylene byfree radical venyl polymerisation.

bioplastics
Biodegradable plastics are plastics that are capable of being decomposed by bacteria or other living organisms. Two basic classes of biodegradable plastics exist:[1] Bioplastics, whose components are derived from renewable raw materials and plastics made from petrochemicals with biodegradable additives which enhance biodegradation.

While aromatic polyesters are almost totally resistant to microbial attack, most aliphatic polyesters are biodegradable due to their potentially hydrolysable ester bonds: Naturally Produced: poly hydroxy butyrate(PHB); Renewable Resource: polylactic acid (PLA); Synthetic: Polybutylene succinate (PBS),)... Most of the starch derivatives Cellulose esters like cellulose acetate and their derivatives Enhanced biodegradable plastic with additives.

Enzymes

are used to break starch in the plants down into glucose, which is fermented and made into lactic acid. This lactic acid is polymerized and converted into a plastic called polylactic acid, which can be used in the manufacture of products after being heated and shaped.

In

addition, bioplastics are biodegradable. If something made of bioplastic is buried in the ground, microorganisms will break it down into carbon dioxide and water. Bags made of bioplastic can be thrown away and buried with other biodegradable garbage, and there are a growing number of other uses for the materials as well, including artificial fibers, medical products, and construction materials.

Use of Bioplastic
Bioplastics

are already being used in automobile interiors and in cases for consumer electronics.

Applications
Packaging

:- The use of bioplastics for shopping bags is already very common. After their initial use they can be reused as bags for organic waste and then be composted. Trays and containers for fruit, vegetables, eggs and meat, bottles for soft drinks and dairy products and blister foils for fruit and vegetables are also already widely manufactured from bioplastics.

Catering

products:- Catering products belong to the group of perishable plastics. Disposable crockery and cutlery, as well as pots and bowls, pack foils for hamburgers and straws are being dumped after a single use, together with foodleftovers, forming huge amounts of waste, particularly at big events.

Gardening: Within

the agricultural economy and the gardening sector mulch foils made of biodegradable material and flower pots made of decomposable bioplastics are predominantly used due to their adjustable lifespan and the fact that these materials do not leave residues in the soil. This helps reduce work and time (and thus cost) as these products can simply be left to decompose, after which they are ploughed in to the soil. Plant pots used for flowering and vegetable plants can be composted along with gardening and kitchen litter.

Sanitary

products:- Due to their specific characteristics, bioplastics are used as a basis for the production of sanitary products. These materials are breathable and allow water vapor to permeate, but at the same time they are waterproof. Foils made of soft bioplastic are already used as diaper foil, bed underlay, for incontinence products, ladies sanitary products and as disposable gloves.

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