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ENGINEERING CHEMISTRY

Polymers: Different methods of classification, basic ideas of polymerization mechanisms. Elastomers: Natural rubber, vulcanization, Synthetic Rubbers viz. Buna-S, Buna-N, Butyl and neoprene rubbers. New Engineering Materials: Fullerenes: Introduction, properties, preparation and uses. Organic Electronic Materials (including conducting polymers- poly (p-phenylene), polythiophenes, Polyphenylene, vinylenes, polypyroles, polyaniline).
1.1 INTRODUCTION: A polymer is a large molecule (macromolecule) composed of repeating structural units. Polymerization is the process of combining many small molecules known as monomers into a covalently bonded chain .

Copolymers The synthesis of macromolecules composed of more than one monomeric repeating unit has been explored as a means of controlling the properties of the resulting material. In this respect, it is useful to distinguish several ways in which different monomeric units might be incorporated in a polymeric molecule. The following examples refer to a two component system, in which one monomer is designated A and the other B. 1.Statistical Copolymers : Also called random copolymers. Here the monomeric units are distributed randomly, and sometimes unevenly, in the polymer chain: ~ABBAAABAABBBABAABA~. 2.Alternating Copolymers:Here the monomeric units are distributed in a regular alternating fashion, with nearly equimolar amounts of each in the chain: ~ABABABABABABABAB~. 3.Block Copolymers:Instead of a mixed distribution of monomeric units, a long sequence or block of one monomer is joined to a block of the second monomer: ~AAAAA-BBBBBBB~AAAAAAA~BBB~. 4.Graft Copolymers: As the name suggests, side chains of a given monomer are attached to the main chain of the second monomer: ~AAAAAAA(BBBBBBB~)AAAAAAA(BBBB~)AAA~.

Classification:
1. Origin or Source : (1)Natural polymer : These polymers are generally obtained from nature. They are available in nature. Examples : Rubber, Cotton, Silk, Wool, Cellulose, Starch, Proteins etc. (2) Semiplastic polymer : They are chemically modified natural polymers. For example cellulose is naturally occurring polymers, cellulose on acetylation with acetic anhydride in the presence of sulphuric acid forms cellulose diacetate polymers. It is used in making thread and materials like films glasses etc. Vulcanized rubber is also an example of semisynthetic polymers used in making tyres etc. gun cotton which is cellulose nitrate used in making explosive. Such as : hydrogeneted , halogeneted or hydro-halogeneted natural rubber cellophane, cellolose, rayon , leather etc. (3) Syntethic polymer : Man made polymers prepared syntheticall from low molecular weight compounds are called synthetic.The polymers which are prepared in the laboratories are called synthetic polymers. These are also called man made polymers. Example: PVC, polyethylene, Polystyrene, nylon etc..

2. Thermal response :
(1) Thermoplastic polymer : Thermoset polymers soften when heated and harden when cooled. Simultaneous application of heat and pressure is required to fabricate these materials. On the molecular level, when the temperature is raised, secondary bonding forces are diminished so that the relative movement of adjacent chains is facilitated when a stress is applied. Most Linear polymers and those having branched structures with flexible chains are thermoplastics. Thermoplastics are very soft and ductile. The commercial available thermoplasts are Polyvinyl Chloride (PVC) and Polystyrene Polymethyl methacrylate Polystyrene

(2) Thermosetting polymer : Thermosetting polymers become soft during their first heating and become permanently hard when cooled. They do not soften during subsequent heating. Hence, they cannot be remolded/reshaped by subsequent heating. In thermosets, during the initial heating, covalent cross-links are formed between adjacent molecular chain. These bonds anchor the chains together to resist the vibration and rotational chain motions at high temperatures. Cross linking is usually extensive in that 10 to 15% of the chain mer units are cross linked. Only heating to excessive temperatures will cause severance of these crosslink bonds and polymer degradation. Thermoset polymers are harder, stronger, more brittle than thermoplastics and have better dimensional stability.They are more usable in processes requiring high temperaturesMost of the cross linked and network polymers which include Vulcanized rubbers,Epoxies,Phenolic,Polyester resins are thermosetting. Thermosets cannot be recycle, do not melt, are usable at higher temperatures than thermoplastics, and are more chemically inert 3. Mode of formation : (1)Addition polymer : An addition polymer is a polymer which is formed by an addition reaction, where many monomers bond together via rearrangement of bonds without the loss of any atom or molecule. Addition polymers have -c-c- linkage along the main chain and no other atom appears in the main chain .They are formed by olefinic diaolefinic mechanism ; known as addition or chain growth polymerization Example: Polyethylene , polypropylene, PVC , polystyrene etc..

(2)Condensation polymers : Condensation polymers are any kind of polymers formed through a condensation reaction, releasing small molecules as by-products such as water or methanol.Condesation polymers are formed from intermolecular reactions between bifunctional or polyfunctional monomer molecules with the elimination of small biproduct molecule.

Example: Polyamides, Polyesters, Polyethers etc.

NYLON:

1. Nylon is a thermoplastic. 2. Nylon is made of repeating units linked by amide bonds and is frequently referred to as polyamide (PA). 3. here are two common methods of making nylon: In one approach, molecules with an acid (COOH) group on each end are reacted with molecules containing amine (-NH2) groups on each end. 4. The general reaction is:

5. Nylon 6,6 is made from the monomers adipoyl chloride and hexamethylene diamine.

6. nylon 6:

Nylon is used to make textile fibres, threads, ropes, toothbrushes and electrical insulators.

THERMO SETTING PLASTICS: (1) BAKELITE: One of the first plastics made from synthetic components, Bakelite was used for its electrically nonconductivity and heat-resistant properties in electrical insulators.

(2)TERYLENE: It is also knoe as polyester.or yerene or decron. A well-known polyester, Terylene, is made by heating ethane-1,2-diol with dimethylbenzene-1,4-dicarboxylate (dimethyl terepthalate):

Terylene is used to make textile fibres, parachutes, stockings, fishing nets and tapes. RUBBER(ELASTOMERS): 1. Natural rubber:Natural rubber is an elastomer (an elastic hydrocarbon polymer) that was originally derived from latex, a milky colloid produced by some plants.

Properties Rubber exhibits unique physical and chemical properties. Rubber's stress-strain behavior exhibits the Mullins effect, the Payne effect, and is often modeled as hyperelastic. Rubber strain crystallizes. Owing to the presence of a double bond in each repeat unit, natural rubber is sensitive to ozone cracking. Natural rubber is often vulcanized, a process by which the rubber is heated and sulfur, peroxide or bisphenol are added to improve resistance and elasticity, 2. Synthetic rubber: Synthetic rubber is any type of artificial elastomer. EXAMPLE: BUNA-N

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