UNIT - 15 POLYMERS

Polymers are the compounds of higher molar mass formed by combination of large number of simple molecules called monomers and the process is called polymerization.
350-570K

n CH2 = CH2 (Ethene)

1000-2000 atm

- ( CH2 = CH2 )n- (Polythene) (Homopolymer)

Homopolymer repeating structural units are derived from one type of monomer unit called homopolymers .e.g. PVC, polyethene etc. Co-polymers: - Structural unit derived from two or more types of monomers called co-polymers.
Polymerisation

nH2N-(CH2)6-NH2+nHOOC-(CH2)2-COOH
(hexamethylenediamine)

- (2n-1) H2O

(Nylon-6, 6-polymer)

A. Classification based on sources NATURAL Found in nature in plants and animals. e.g. proteins, natural rubbers etc. SEMISYNTHETIC SYNTHETIC Polymers are prepared by Man-made in Lab. E.g. some modification in nylon, polyethene etc. natural polymers. E.g. nitrocellulose etc.

A. Classification based on structure 1. Linear polymers-polymers having long chain and straight chain. e.g.PVC, nylon etc. 2. Branched chain-having linear chains with some branches. E.g. low density polyethene, glycol etc.

3. Cross linked or Network polymer- Generally formed from bi-functional or tri-functional monomers and has strong covalent bonds between various linear polymer chains. E.g. Bakelite, melamine etc. The polymers are hard, rigid and brittle.

A. Classification based on mode of

polymerization

1. Addition polymers- These polymers are formed by the repeated addition of some or different monomer molecules having double or triple bonds e.g. polyethene etc. 2. Condensation polymers and condensation polymerization-formed by repeated condensation reaction between different bi-functional or tri-functional monomer units, usually one small molecules like alcohol, HCl, H2O etc.
Polymerisation

nH2N-(CH2)6-NH2+nHOOC-(CH2)2-COOH
(hexamethylenediamine)

- (2n-1) H2O

(Nylon-6, 6-polymer)

CLASSIFICATION BASED ON MOLECULAR FORCES:Elastomers- Polymers having weakest intermolecular forces of attraction between polymer chains. Due to these weakest forces, polymers can be stretched. Low cross links are introduced in between the chains, which help the polymers to retain its original position after force is released. E.g. vulcanized rubber e.g. Buna-S-, Buna-H-, neoprene etc. Fibres- They have the strongest intermolecular forces such as H-bond or dipole-dipole interactions. These polymers can be used to make fibres as their molecules are long and thread like. Nylon 6-6, terylener are common examples. Thermoplastics-have intermolecular forces of attraction between elastomers and fibres. They are linear or slightly branched chain polymers. They become soft on repeatedly heating and attain hardness on further cooling. E.g. polyethene, polystyrene etc. Thermosetting- These polymers are cross linked or heavily branched molecules, which on heating undergo extensive cross linking in moulds and again become infusible. These polymers cant be reshaped e.g. Bakelite, urea formaldehyde refins etc.

THERMOPLASTIC -These soften and melt on heating -Formed by addition polymerization. -Usually have linear structures.

-Can be remolded, recast, and reshaped. -Less brittle and soluble in some organic -More brittle and insoluble in organic solvents solvents. -Teflon , PVC ,nylon ,polyethylene - Bakelite, urea formaldehyde refins etc.

THERMOSETTING -Do not soften but become hard. On strong heating it start to burn. - Formed by condensation polymerization. -Three dimensional cross-linked structures. -No

Types of Polymerisation Reactions A. Addition polymerization or chain growth polymerization Involve successive addition of monomer units to the growing chain carrying a reactive intermediate such as free radical or anion. Three types on the nature of reacting species a. Free radical polymerization: - alkenes or dienes and their derivatives are polymerized in presence of a free radical generating initiator (catalyst) like benzoyl peroxide. Acetyl peroxide, tert butyl peroxide etc. E.g. ethane polythene O O || || (C6H5CO)2O2 Or C6H5-C-O-O-C-C6H5
Benzoyl peroxide

2C6H5
Phenyl radical

-2CO2

(Initiator)

Indicator

Monomer

b. Chain propagation:-

C6H5-CH2-CH2+CH2=CH2

C6H5-CH2-CH2-CH2-CH2 C6H5-(CH2-CH2)n-CH2-CH2
(Intermediate)

c. Chain Termination:- Two molecules of intermediate combined together combine together to give polymer. 2C6H5-(CH2-CH2)n-CH2-CH2 C6H5-(CH2-CH2)n-CH2-CH2 CH2-CH2-(CH2-CH2-)n-C6H5
Polythene (polymer)

CH2=CH Cl
Vinyl Chloride polymer

-(CH2-CH)nCl

PVC Polymer (Repeating units)

CH2=CH CN
Aerylo nitrile

-(CH2-CH)nCN

Poly Aerylo nitrile (PAN)

Preparation of some Important Addition Polymers :B. Polythene : (Polyethylene):a. Low density Polythene: - (LDP) - It is obtained by polymerization of ethene under high pressure (1000-2000atm) temp 350 to 510K in presence of traces of O2 or any peroxide intiator.LDP is obtained through free radical addition and H-atom abstraction is highly branched structure.

350-570K and 1000-200 atm

n CH2 = CH2

traces of O2

- ( CH2 = CH2 )n- (LDP)

These are chemically inert, tough and flexible, poor conductors of electricity. b. Prepared by co-ordination polymerization of ethene. Here ethene is heated to 333343K at 6-7 atm pressure in presence of catalyst i.e. Triethyl aluminium and TiCl4 or TiCl3
333-343K and 6-7 atm

n CH2 = CH2

(C2H5)3Al / TiCl4

- ( CH2 = CH2 )n- (HDP)

It is translucent, chemically inert, highly tough, hard and high tensile strength. Used in, manufacturing of container, house wires, pipes, bottles and toys.

Polypropene :-

Used in manufacturing of toys, ropes, pipes, carpet fibers etc. Polystyrene or Styrone :-

Used as insulator, wrapping material, manufacture of toys, radio & TV cabinets.

Tetraflouroethene [Teflon]-

n CF2=CF2
(Terta fluoroethene)

Catalyst

- (CF2-CF2) n-

(Polytetra flouroethene)

It is very tough material and resistant towards heat action of acids or bases. It is bad conductor of electricity. Due to high chemical inertness and high thermal stability, Teflon is used for making non-stick utensils, gaskets etc. Poly Aerylonitrile (PAN) CH2=CH CN
Aerylo nitrile
Peroxide Catalyst

- (CH2-CH) nCN

Poly Aerylo nitrile

It is used as a substitute for wool in making fibres called Orlon or aerilan. Co-Polymerisation:- More than 1-monomer is allowed to polymerize. nCH2=CH-CH-CH2 + nCH2=CH2
(1,3-butadiene)

- (CH2-CH=CH-CH2-CH-CH2)(co-polymer)

C6H5

(styrene)

C6H5

Co-Polymers have different properties from homopolymers. E.g. polysterene,a homopolymers of styrene is a good insulator and is used for making toys, T.V cabinets etc.Whereas styrenebutadiene rubber, a co-polymer of styrene and butadiene, is a good substitute for rubber and is used for making automobile tyres,cable insulators etc.

Condensation polymerization or step growth polymerization It involves repetitive condensation of different or same monomers having bi-functional group. At every stage a small molecule like H2O is lost. 1. Polyamides polymers possessing amide linkage are called polyamides. Prepared by condensation polymerization of dibasic acids with diamines or their equivalents. (a) Nylon 6,6 prepared by condensation polymerisation of hexa methylenediamine with Adipic Acid under high pressure and temperature.

nHOOC-(CH2)4-COOH + nH2N-(CH2)6-NH2

(2n-1)H2O +

Ques. Why it is called nylon-6, 6? Ans. It is because both acid and amine contains 6C atoms. - It is used in making sheets, bristles for brushes and in textile industry.

Nylon-6- (Terlon) :- prepared from single monomer having a potential amino group at one end and potential carxyl group at the other.

- Used in manufacturing of tyre cords, fabrics and ropes. Polyester: - having ester linkages are called polyesters and are prepared by condensation polymerization of di-acids with di-oils. 1. Terylene or Decron

- Used to make wash and wear fabric tyre cords, sails and seatbelts.

2. Glyptal

Glyptal Used in manufacturing of paints & lacquered. Cross Linked Polymer: Phenol formaldehyde polymer (Bakelite): - It is formed by condensation of phenol with formaldehyde in presence of an acid or base.

Bakelite is hard, scratch resistant as well as water resistant polymer, insulator. Hence, it is used for making electrical goods (switcher etc.) gramophone records, handler etc. Melamine formaldehyde Polymer: It is co-polymer of melamine and formaldehyde. It is formed by condensation, polymerization of Melamine and formaldehyde.

Used to make unbreakable crockery. Co Polymerisation: Two or more different monomers are allowed to polymerise together, product is called co polymer and process co polymerisation.

Very tough and good substitute of natural Rubber. High Tensile strength, used to make automobile tiers. Used for making floor or tiles, footwear components, cable insulation etc. Rubber: A. Natural Rubber It is a natural polymer, has remarkable elasticity, reversible even after applying small force. It is called elastomers. Manufactured form rubber latex which is a colloidal dispersion rubber in water. Natural rubber is a linear polymer of Isoprene.

Natural Rubber

The cis polyisoprene molecule consists of various chains held together by weak Van der Waals interaction and has coiled structure. It can be stretched like a spring and exhibits elastic properties.

Trans polyisoprene [Gutta Percha] B. Vulcanised Rubber Natural become soft at high temperature and brittle at low temperature. It is non resistant to polar solvents and is easily attacked by oxidizing agents. Addition of sulphur to heat rubber improves its properties. This process is called Vulcanisation.

During vulcanisation, sulphur forms cross-links of the reactive sites (at allylic positions). Vulcanised rubber shows improved properties1. Rubber gets stiffened. 2. Has a low H2O absorbtion property. 3. Resistant to oxidation & organic solvents. 4. It is hard, tough & has high tensile strength. Amount of sulphur decides the properties of vulcanised rubber. 5% sulphur contains vulcanised rubber used to make automobiles tiers. 30% used in battery case rubber.

C. Synthetic Rubber Synthetic rubbers are either Homopolymers of 1, 3-butadiene derivatives with another unsaturated monomer.

Neoprene:-

Used in the manufacturing conveyer belts gaskets and hoses. Resistant to vegetables and mineral oils. Buna N:Co Polymer of 1, 3-butadiene and Acrylonitrile in presence of peroxide catalyst.

Resistant to the action of petrol, lubricating oil and used in making oil seals and for tank lining.

BIODEGRADABLE POLYMERS Biodegradable Polymers are those which can be broken into small segments by enzyme catalyzed reaction. In biological system polymers are degraded mainly by enzyme hydrolysis or sometimes by oxidation. Biodegradable synthetic polymers have functional group similar to natural polymers. The C-C bonds of chain growth polymers (polymers etc.) are inter to enzyme action. Therefore, they are non-biodegradable. Certain groups like easily hydrolysable ester group, etc. are introduced which can be hydrolysed. e.g. i. PHBV [Poly hydroxyl butyrate CO - hydroxyl valerate]

It is a co-polymer of 3 hydroxy butanoic acid and 3 hydroxyl pentanoic acid

This is used for special packing, orthopaedic device and slow release in formulation of medicines.

ii. COOH | COOH

Polyglycolic Acid & Polyactic Acid OH | CH3 CH COOH

(glycolic acid)

(Lactic acid)

They are used as Sutures (post operative stiches). iii. Nylon 2 Nylon 6

It is an alternating poly amide. It is a co-polymer of Glycene and - Amino Caproic acid. [ - on 6th C atom (like , , , etc.]

It is also biodegradable.

SOME COMMON IMPORTANT POLYMERS

ADDITION POLYMERS
1 POLYTHENE Ethene i. ii. iii. as an insulator Packing material Containers

CH2=CH2 2 POLYPROPENE Propene Manufacture of ropes, toys, pipes, fibers etc.

CH3-CH=CH2 3 POLYSTYRENE Styrene For making toys, TV cabinets as insulator.

POLYVINYLCHLORIDE

Vinyl chloride

For making raincoats, pipes, vinyl flooring etc.

CH2=CH-Cl 5 TEFLON Tetrafluoroethene For making gaskets oil seals, non-stick cookware etc.

CF2=CF2 Polytetrafluoroethene 6 NEOPRENE Chloroprene For making hoses, gaskets, conveyer belts etc.

BUNA-S SBR or Styrene Butadiene Copolymer.

Butadiene CH2=CH-CH=CH2 & Styrene

For making automobile tiers waterproof shoes, rubber soles etc.

BUNA-N (nitrile rubber)

Butadiene CH2=CH-CH=CH2 & Acrylonitrile CH2CH-CN

For making oil-seals, hoses, tank-linings.

PMMA Polymethylmetacrylate

Methyl methacrylate

Uses for making lenses, aircraft, windows, transparent domes.

10

POLYACRYLONITRILE (PAN)

Acrylonitrile

For making synthetic fibers & wool, carpets and blankets.

ORLON ACRYLAN

CONDENSATION POLYMERS
(A)
1

POLYSTERS
TERYLENE OR DACTRON i. Ethylene glycol HOCH2-CH2OH ii. Terephthalic acid For making crease-resistance fibers as blend with cotton & wool for making seat belts, sails.

GLYPTAL (Alkyd Resins)

i. Ethylene glycol HOCH2-CH2OH ii. Phthalic acid

Used in the manufacture of paints & lacquers.

(B)
1

POLYAMIDES
NYLON - 6,6 i. Adipic acid Used in manufacture of textile fabrics, HOOC-(CH2)4-COOH ropes, bristles for brushes. ii. Hexamethylenediamine H2N-(CH2)6-NH2 Caprolactam Used for making tyre cords.

NYLON 6

THERMOSETTING POLYMERS -RESINS

1 Phenol formaldehyde resin i. Phenol For making combs, phonograph records, electrical switches & handles for utensils.

ii.

Formaldehyde HCHO

Melamine formaldehyde resin

i.

Melamine

For making unbreakable cookware.

ii. 3 Urea formaldehyde resin i. ii.

Formaldehyde HCHO Urea For making laminated sheets, H2N-CO-NH2 unbreakable cups. Formaldehyde HCHO